Sample records for relevant concentrations reaction

  1. Reaction of tetracycline with biologically relevant chloramines

    Benavides, J.; Barrias, P.; Piro, N.; Arenas, A.; Orrego, A.; Pino, E.; Villegas, L.; Dorta, E.; Aspée, A.; López-Alarcón, C.


    Helicobacter pylori (H. pylori) infection triggers inflammatory processes with the consequent production of hypochlorous acid (HOCl), monochloramine (NH2Cl), and protein-derived chloramines. As the therapy for eradicating H. pylori is partially based on the use of tetracycline, we studied the kinetic of its consumption elicited by HOCl, NH2Cl, N-chloro-n-butylamine (NHCl-But, used as a lysine-derived chloramine model), and lysozyme-derived chloramines. In the micromolar concentration range, tetracycline reacted rapidly with HOCl, generating in the first few seconds intermediates of short half-life. In contrast, a slow tetracycline consumption was observed in the presence of high NH2Cl and NHCl-But concentrations (millimolar range). Similar chlorinated products of tetracycline were identified by mass spectrometry, in the presence of HOCl and NH2Cl. These results evidenced that tautomers of tetracycline are pivotal intermediates in all reactions. In spite of the low reactivity of chloramines towards tetracycline, it is evident that, in the concentration range where they are produced in a H. pylori infection (millimolar range), the reactions lead to oxidation and/or chlorination of tetracycline. This kind of reactions, which were also observed triggered by lysozyme-derived chloramines, could limit the efficiency of the tetracycline-based therapy.

  2. Autocatalytic, bistable, oscillatory networks of biologically relevant organic reactions

    Semenov, Sergey N.; Kraft, Lewis J.; Ainla, Alar; Zhao, Mengxia; Baghbanzadeh, Mostafa; Campbell, Victoria E.; Kang, Kyungtae; Fox, Jerome M.; Whitesides, George M.


    Networks of organic chemical reactions are important in life and probably played a central part in its origin. Network dynamics regulate cell division, circadian rhythms, nerve impulses and chemotaxis, and guide the development of organisms. Although out-of-equilibrium networks of chemical reactions have the potential to display emergent network dynamics such as spontaneous pattern formation, bistability and periodic oscillations, the principles that enable networks of organic reactions to develop complex behaviours are incompletely understood. Here we describe a network of biologically relevant organic reactions (amide formation, thiolate-thioester exchange, thiolate-disulfide interchange and conjugate addition) that displays bistability and oscillations in the concentrations of organic thiols and amides. Oscillations arise from the interaction between three subcomponents of the network: an autocatalytic cycle that generates thiols and amides from thioesters and dialkyl disulfides; a trigger that controls autocatalytic growth; and inhibitory processes that remove activating thiol species that are produced during the autocatalytic cycle. In contrast to previous studies that have demonstrated oscillations and bistability using highly evolved biomolecules (enzymes and DNA) or inorganic molecules of questionable biochemical relevance (for example, those used in Belousov-Zhabotinskii-type reactions), the organic molecules we use are relevant to metabolism and similar to those that might have existed on the early Earth. By using small organic molecules to build a network of organic reactions with autocatalytic, bistable and oscillatory behaviour, we identify principles that explain the ways in which dynamic networks relevant to life could have developed. Modifications of this network will clarify the influence of molecular structure on the dynamics of reaction networks, and may enable the design of biomimetic networks and of synthetic self-regulating and evolving

  3. Locating conical intersections relevant to photochemical reactions

    Dick, Bernhard [Institut fuer Physikalische und Theoretische Chemie, Universitaet Regensburg, D 93040 Regensburg (Germany)], E-mail:; Haas, Yehuda; Zilberg, Shmuel [Department of Physical Chemistry and the Farkas Center for Light-induced Processes, The Hebrew University of Jerusalem, Jerusalem 91904 (Israel)


    A new computerized method for locating conical intersections of interest in photochemistry is presented. The search is based on the Longuet-Higgins phase change theorem (Berry phase) which provides the subspace required for the initial search. The subspace is approximated as a plane containing three stable structures lying on a Longuet-Higgins loop. The search is conducted for a minimum of {delta}E, the energy difference between two electronic states. It is started using up to three points within the circle defined by the three structures; symmetry, if relevant, is helpful but not essential. Since a two-dimensional subspace of the large 3N - 6 space is used, the search that uses either Cartesian or internal coordinates is efficient and yields a degeneracy after a few iterations. Given that not all degrees of freedom are included in the search, usually a high lying part of the conical intersection is initially located. The system is subsequently optimized along all coordinates keeping {delta}E as close to zero as desired. The method is demonstrated for the symmetric H{sub 3} system and also for the butadiene-cyclobutene-bicyclobutane system in which the three stable structures are not equivalent. The method is general and can be extended to any photochemical system.

  4. Acrosome reaction: relevance of zona pellucida glycoproteins

    Satish K Gupta; Beena Bhandari


    During mammalian fertilisation,the zona pellucida(ZP)matrix surrounding the oocyte is responsible for the binding of the spermatozoa to the oocyte and induction of the acrosome reaction(AR)in the ZP-bound spermatozoon.The AR is crucial for the penetration of the ZP matrix by spermatozoa.The ZP matrix in mice is composed of three glycoproteins designated ZP1,ZP2 and ZP3,whereas in humans,it is composed of four(ZP1,ZP2,ZP3 and ZP4).ZP3 acts as the putative primary sperm receptor and is responsible for AR induction in mice,whereas in humans(in addition to ZP3),ZP1 and ZP4 also induce the AR.The ability of ZP3 to induce the AR resides in its C-terminal fragment.O-linked glycans are critical for the murine ZP3-mediated AR.However,N-linked glycans of human ZP1,ZP3 and ZP4 have important roles in the induction of the AR.Studies with pharmacological inhibitors showed that the ZP3-induced AR involves the activation of the G1-coupled receptor pathway,whereas ZP1-and ZP4-mediated ARs are independent of this pathway.The ZP3-induced AR involves the activation of T-type voltage-operated calcium channels(VOCCs),whereas ZP1-and ZP4-induced ARs involve both T-and L-type VOCCs.To conclude,in mice,ZP3 is primarily responsible for the binding of capacitated spermatozoa to the ZP matrix and induction of the AR,whereas in humans(in addition to ZP3),ZP1 and ZP4 also participate in these stages of fertilisation.

  5. Relevance of positive patch-test reactions to fragrance mix

    Devos, S.A.; Constandt, L.; Tupker, R.A.; Noz, K.C.; Lucker, G.P.H.; Bruynzeel, D.P.; Schuttelaar, M.L.A.; Kruyswijk, M.R.J.; van Zuuren, E.J.; Vink, J.; Coenraads, P.J.; Kiemeney, L.A.L.M.; van der Valk, P.G.M.


    BACKGROUND: Fragrances are an important cause of allergic contact dermatitis. We presume that the traditional fragrance mix (FM) detects 70 to 80% of fragrance-allergic patients. FM has an irritant potential. Weak positive reactions may have a greater chance of being irrelevant than strong reactions

  6. Relevance of positive patch-test reactions to fragrance mix.

    Devos, S.A.; Constandt, L.; Tupker, R.A.; Noz, K.C.; Lucker, G.P.H.; Bruynzeel, D.P.; Schuttelaar, M.L.; Kruyswijk, M.R.; Zuuren, E.J. van; Vink, J.; Coenraads, P.J.; Kiemeney, L.A.L.M.; Valk, P.G.M. van der


    BACKGROUND: Fragrances are an important cause of allergic contact dermatitis. We presume that the traditional fragrance mix (FM) detects 70 to 80% of fragrance-allergic patients. FM has an irritant potential. Weak positive reactions may have a greater chance of being irrelevant than strong reactions

  7. PTEN Mediates the Antioxidant Effect of Resveratrol at Nutritionally Relevant Concentrations

    Marta Inglés


    Full Text Available Introduction. Antioxidant properties of resveratrol have been intensively studied for the last years, both in vivo and in vitro. Its bioavailability after an oral dose is very low and therefore it is very important to make sure that plasma concentrations of free resveratrol are sufficient enough to be active as antioxidant. Aims. In the present study, using nutritionally relevant concentrations of resveratrol, we aim to confirm its antioxidant capacity on reducing peroxide levels and look for the molecular pathway involved in this antioxidant effect. Methods. We used mammary gland tumor cells (MCF-7, which were pretreated with different concentrations of resveratrol for 48 h, and/or a PTEN inhibitor (bpV: bipy. Hydrogen peroxide levels were determined by fluorimetry, PTEN levels and Akt phosphorylation by Western Blotting, and mRNA expression of antioxidant genes by real-time reverse transcriptase-polymerase chain reaction (RT-PCR. Results. Resveratrol treatment for 48 h lowered peroxide levels in MCF-7, even at low nutritional concentrations (1 nM. This effect was mediated by the activation of PTEN/Akt pathway, which resulted in an upregulation of catalase and MnSOD mRNA levels. Conclusion. Resveratrol acts as an antioxidant at nutritionally relevant concentrations by inducing the expression of antioxidant enzymes, through a mechanism involving PTEN/Akt signaling pathway.

  8. Relevance of positive patch-test reactions to fragrance mix

    Devos, S.A.; Constandt, L.; Tupker, R.A.; Noz, K.C.; Lucker, G.P.H.; Bruynzeel, D.P.; Schuttelaar, M.L.A.; Kruyswijk, M.R.J.; van Zuuren, E.J.; Vink, J.; Coenraads, P.J.; Kiemeney, L.A.L.M.; van der Valk, P.G.M.


    BACKGROUND: Fragrances are an important cause of allergic contact dermatitis. We presume that the traditional fragrance mix (FM) detects 70 to 80% of fragrance-allergic patients. FM has an irritant potential. Weak positive reactions may have a greater chance of being irrelevant than strong

  9. Sulindac sulfide suppresses 5-lipoxygenase at clinically relevant concentrations.

    Steinbrink, Svenja D; Pergola, Carlo; Bühring, Ulrike; George, Sven; Metzner, Julia; Fischer, Astrid S; Häfner, Ann-Kathrin; Wisniewska, Joanna M; Geisslinger, Gerd; Werz, Oliver; Steinhilber, Dieter; Maier, Thorsten J


    Sulindac is a non-selective inhibitor of cyclooxygenases (COX) used to treat inflammation and pain. Additionally, non-COX targets may account for the drug's chemo-preventive efficacy against colorectal cancer and reduced gastrointestinal toxicity. Here, we demonstrate that the pharmacologically active metabolite of sulindac, sulindac sulfide (SSi), targets 5-lipoxygenase (5-LO), the key enzyme in the biosynthesis of proinflammatory leukotrienes (LTs). SSi inhibited 5-LO in ionophore A23187- and LPS/fMLP-stimulated human polymorphonuclear leukocytes (IC(50) approximately 8-10 microM). Importantly, SSi efficiently suppressed 5-LO in human whole blood at clinically relevant plasma levels (IC(50) = 18.7 microM). SSi was 5-LO-selective as no inhibition of related lipoxygenases (12-LO, 15-LO) was observed. The sulindac prodrug and the other metabolite, sulindac sulfone (SSo), failed to inhibit 5-LO. Mechanistic analysis demonstrated that SSi directly suppresses 5-LO with an IC(50) of 20 muM. Together, these findings may provide a novel molecular basis to explain the COX-independent pharmacological effects of sulindac under therapy.

  10. Prevention of febrile nonhemolytic transfusion reaction with leucocyte filtrated concentrates

    ZHAO Shu-ming; XIANG Guo-chun; ZHANG Jia-si; CHENG Xiao-ling; LI Ru-qing


    Objective: To assess the clinical efficiency of the transfusion of leucocyte filtrated RBC concentrates to prevent febrile nonhemolytic transfusion reactions (FNHTRs). Methods: One hundred patients with liver cirrhosis, gastric ulcer or cancer were subjected to receive RBC concentrates after leucocyte filtration.Another 50 patients with similar diseases were selected to receive non-filtrated RBC concentrates. The incidence of FNHTRs in all patients was investigated. Results: There was no FNHTR in 100 transfusions with leucocyte filtrated RBC concentrates, while FNHTRs occurred in 8 of 50 patients with non-filtrated RBC concentrates, with the incidence of 160%. Conclusion: FNHTRs to RBC transfusion can be prevented with leucocyte filtration.

  11. Reaction Profiles and Molecular Dynamics Simulations of Cyanide Radical Reactions Relevant to Titan's Atmosphere

    Trinidad Pérez-Rivera, Danilo; Romani, Paul N.; Lopez-Encarnacion, Juan Manuel


    Titan's atmosphere is arguably the atmosphere of greatest interest that we have an abundance of data for from both ground based and spacecraft observations. As we have learned more about Titan's atmospheric composition, the presence of pre-biotic molecules in its atmosphere has generated more and more fascination about the photochemical process and pathways it its atmosphere. Our computational laboratory has been extensively working throughout the past year characterizing nitrile synthesis reactions, making significant progress on the energetics and dynamics of the reactions of .CN with the hydrocarbons acetylene (C2H2), propylene (CH3CCH), and benzene (C6H6), developing a clear picture of the mechanistic aspects through which these three reactions proceed. Specifically, first principles calculations of the reaction profiles and molecular dynamics studies for gas-phase reactions of .CN and C2H2, .CN and CH3CCH, and .CN and C6H6 have been carried out. A very accurate determination of potential energy surfaces of these reactions will allow us to compute the reaction rates which are indispensable for photochemical modeling of Titan's atmosphere.The work at University of Puerto Rico at Cayey was supported by Puerto Rico NASA EPSCoR IDEAS-ER program (2015-2016) and DTPR was sponsored by the Puerto Rico NASA Space Grant Consortium Fellowship. *E-mail:

  12. An experimental and theoretical study of reaction steps relevant to the methanol-to-hydrocarbons reaction

    Svelle, Stian


    The primary objective of the present work is to obtain new insight into the reaction mechanism of the zeolite catalyzed methanol-to-hydrocarbons (MTH) reaction. It was decided to use both experimental and computational techniques to reach this goal. An investigation of the n-butene + methanol system was therefore initiated. Over time, it became apparent that it was possible to determine the rate for the methylation of n-butene by methanol. The ethene and propene systems were therefore reexamined in order to collect kinetic information also for those cases. With the development of user-friendly quantum chemistry programs such as the Gaussian suite of programs, the possibility of applying quantum chemical methods to many types of problems has become readily available even for non-experts. When performing mechanistic studies, there is quite often a considerable synergy effect when combining experimental and computational approaches. The methylation reactions mentioned above turned out to be an issue well suited for quantum chemical investigations. The incentive for examining the halomethane reactivity was the clear analogy to the MTH reaction system. Alkene dimerization was also a reaction readily examined with quantum chemistry. As discussed in the introduction of this thesis, polymethylbenzenes, or their cationic counterparts, are suspected to be key intermediates in the MTH reaction. It was therefore decided to investigate the intrinsic reactivity of these species in the gas-phase by employing sophisticated mass spectrometric (MS) techniques in collaboration with the MS group at the Department of Chemistry, University of Oslo The data thus obtained will also be compared with results from an ongoing computational study on gas phase polymethylbenzenium reactivity. 6 papers presenting various studies are included. The titles are: 1) A Theoretical Investigation of the Methylation of Alkenes with Methanol over Acidic Zeolites. 2) A Theoretical Investigation of the

  13. The Value Relevance of Earnings and Book Value: The Importance of Ownership Concentration and Firm Size

    Pathirawasam Chandrapala


    Full Text Available The purpose of this paper is to investigate the impact of ownership concentration and firm size on value relevance of two accounting variables, earnings and book value, given by firms listed in Colombo Stock Exchange (CSE in Sri Lanka from 2005 to 2009. Using pooled cross-sectional data regressions, the study finds that the value relevance of earnings and book value is below average. The value relevance of ownership concentrated firms is higher than that of ownership non-concentrated firms. Further, the two variables show higher value relevance for larger firms than for smaller firms. Contrary to the previous findings of the author, the study finds that book value is more value relevant than the earnings in Sri Lanka.

  14. Transport of Fluorescently Labeled Hydroxyapatite Nanoparticles in Saturated Granular Media at Environmentally Relevant Concentrations of Surfactants

    Little is known about the mobility of engineered nanoparticles (ENPs) in granular media at environmentally relevant concentration of surfactant, which represents a critical knowledge gap in employing ENPs for in-situ remediation of contaminated groundwater. In this study, transpo...

  15. The Value Relevance of Earnings and Book Value: The Importance of Ownership Concentration and Firm Size

    Chandrapala Pathirawasam


      The purpose of this paper is to investigate the impact of ownership concentration and firm size on value relevance of two accounting variables, earnings and book value, given by firms listed in Colombo Stock Exchange (CSE...

  16. The Value Relevance of Earnings and Book Value: The Importance of Ownership Concentration and Firm Size

    Pathirawasam, Chandrapala


    The purpose of this paper is to investigate the impact of ownership concentration and firm size on value relevance of two accounting variables, earnings and book value, given by firms listed in Colombo Stock Exchange (CSE...

  17. Gas-phase Reactions of Polycyclic Aromatic Hydrocarbon Anions with Molecules of Interstellar Relevance

    Demarais, Nicholas J.; Yang, Zhibo; Martinez, Oscar; Wehres, Nadine; Snow, Theodore P.; Bierbaum, Veronica M.


    We have studied reactions of small dehydrogenated polycyclic aromatic hydrocarbon anions with neutral species of interstellar relevance. Reaction rate constants are measured at 300 K for the reactions of phenide (C6H- 5), naphthalenide (C10H- 7), and anthracenide (C14H- 9) with atomic H, H2, and D2 using a flowing afterglow-selected ion flow tube instrument. Reaction rate constants of phenide with neutral molecules (CO, O2, CO2, N2O, C2H2, CH3OH, CH3CN, (CH3)2CO, CH3CHO, CH3Cl, and (CH3CH2)2O) are also measured under the same conditions. Experimental measurements are accompanied by ab initio calculations to provide insight into reaction pathways and enthalpies. Our measured reaction rate constants should prove useful in the modeling of astrophysical environments, particularly when applied to dense regions of the interstellar and circumstellar medium.

  18. The Trojan Horse Method as a tool for investigating astrophysically relevant fusion reactions

    Lamia, L.; Spitaleri, C.; Tognelli, E.; Degl'Innocenti, S.; Pizzone, R. G.; Prada Moroni, P. G.


    The Trojan Horse Method (THM) has been largely adopted for investigating astrophysically relevant charged-particle induced reactions at Gamow energies. Indeed, THM allows one to by pass extrapolation procedures, thus overcoming this source of uncertainty. Here, the recent THM results and their impact in astrophysics are going to be discussed.

  19. Simultaneous measurement of reactions in microdroplets filled by concentration gradients.

    Damean, Nicolae; Olguin, Luis F; Hollfelder, Florian; Abell, Chris; Huck, Wilhelm T S


    This work describes a technology for performing and monitoring simultaneously several reactions confined in strings of microdroplets having identical volumes but different composition, and travelling with the same speed in parallel channels of a microfluidic device. This technology, called parallel microdroplets technology (PmicroD), uses an inverted optical microscope and a charge-coupled device (CCD) camera to collect images and analyze them so as to report on the reactions occurring in these microdroplets. A concentration gradient of one reactant is created in the microfluidic device. In each channel, a different concentration of this reactant is mixed with a fixed amount of a second reactant. Using planar flow-focusing methodology, these mixtures are confined in microdroplets of pL size which travel in oil as continuous medium, avoiding laminar dispersion. By analyzing the images of parallel strings of microdroplets, the time courses of several reactions with different reagent compositions are investigated simultaneously. In order to design the microfluidic device that consists in a complex network of channels having well-defined geometries and restricted positions, the theoretical concept of equivalent channels (i.e. channels having identical hydraulic resistance) is exploited and developed. As a demonstration of the PmicroD technology, an enzyme activity assay was carried out and the steady-state kinetic constants were determined.

  20. Capture reactions of astrophysical relevance in the CNO-cycles and in stellar helium burning

    Hammer, J W; Jäger, M; Kunz, R; Mayer, A; Morlock, R; Schreiter, R; Staudt, G; Mohr, P J; Butt, Y; Parker, P D; Kratz, K L; Pfeiffer, B


    In the DYNAMITRON laboratory of the University of Stuttgart capture reactions have been investigated which are important for the nucleosynthesis of the elements. Various stellar models describing nucleosynthesis require nuclear reaction rates at burning temperatures with sufficient accuracy. Applying techniques of high sensitivity to cross section measurements one is straining to extend these measurements as far as possible into the astrophysically relevant range at low energies. But despite all these efforts one often has to apply extrapolations or one has to investigate mirror nuclei in cases where the target nucleus is not available in sufficient amounts.

  1. A Pilot Study of Ion - Molecule Reactions at Temperatures Relevant to the Atmosphere of Titan

    Zymak, Illia; Žabka, Ján; Polášek, Miroslav; Španěl, Patrik; Smith, David


    Reliable theoretical models of the chemical kinetics of the ionosphere of Saturn's moon, Titan, is highly dependent on the precision of the rates of the reactions of ambient ions with hydrocarbon molecules at relevant temperatures. A Variable Temperature Selected Ions Flow Tube technique, which has been developed primarily to study these reactions at temperatures within the range of 200-330 K, is briefly described. The flow tube temperature regulation system and the thermalisation of ions are also discussed. Preliminary studies of two reactions have been carried out to check the reliability and efficacy of kinetics measurements: (i) Rate constants of the reaction of CH3 + ions with molecular oxygen were measured at different temperatures, which indicate values in agreement with previous ion cyclotron resonance measurements ostensibly made at 300 K. (ii) Formation of CH3 + ions in the reaction of N2 + ions with CH4 molecules were studied at temperatures within the range 240-310 K which showed a small but statistically significant decrease of the ratio of product CH3 + ions to reactant N2 + ions with reaction temperature.

  2. Self-relevance appraisal influences facial reactions to emotional body expressions.

    Julie Grèzes

    Full Text Available People display facial reactions when exposed to others' emotional expressions, but exactly what mechanism mediates these facial reactions remains a debated issue. In this study, we manipulated two critical perceptual features that contribute to determining the significance of others' emotional expressions: the direction of attention (toward or away from the observer and the intensity of the emotional display. Electromyographic activity over the corrugator muscle was recorded while participants observed videos of neutral to angry body expressions. Self-directed bodies induced greater corrugator activity than other-directed bodies; additionally corrugator activity was only influenced by the intensity of anger expresssed by self-directed bodies. These data support the hypothesis that rapid facial reactions are the outcome of self-relevant emotional processing.

  3. Experimental evidence of the relevance of orientational correlations in photoinduced bimolecular reactions in solution.

    Angulo, Gonzalo; Cuetos, Alejandro; Rosspeintner, Arnulf; Vauthey, Eric


    A major problem in the extraction of the reaction probability in bimolecular processes is the disentanglement from the influence of molecular diffusion. One of the strategies to overcome it makes use of reactive solvents in which the reactants do not need to diffuse to encounter each other. However, most of our quantitative understanding of chemical reactions in solution between free partners is based on the assumption that they can be approximated by spheres because rotation averages their mutual orientations. This condition may not be fulfilled when the reaction takes place on time scales faster than that of molecular reorientation. In this work, the fluorescence quenching of two very similar polyaromatic hydrocarbons with different electric dipole moments is measured. The concentration of a liquid electron-donating quencher is varied from very dilute solutions to pure quencher solutions. In both cases, the thermodynamics of the reactions are very similar and, according to the Marcus expression, the kinetics are expected to proceed at similar rates. However, one of them is 10 times faster in the pure quencher solution. This difference starts at relatively low quencher concentrations. An explanation based on the fluorophore-solvent dipole-dipole interaction and the consequent orientational solvent structure is provided. The orientational correlation between fluorophore and quencher is calculated by means of computer simulations. Important differences depending on the fluorophore dipole moment are found. The kinetics can be explained quantitatively with a reaction-diffusion model that incorporates the effects of the presence of the dipole moment and the rotational diffusion, only in the highest quencher concentration case, but not in dilute solutions, most likely due to fundamental limitations of the kinetic theory.

  4. Physiological responses and gene expression changes in the western mosquitofish (Gambusia affinis) exposed to progesterone at environmentally relevant concentrations.

    Hou, Liping; Xu, Hongyan; Ying, Guangguo; Yang, Yang; Shu, Hu; Zhao, Jianliang; Cheng, Xuemei


    Progesterone (P4) is a natural and synthetic steroid, widely distributed in the aquatic environments. It can lead to adverse effects on the endocrine system in aquatic organisms. This study investigated the toxicological effects of exposure to environmentally relevant concentrations (4, 44, and 410ng/L) of progesterone for 42 d on adult female mosquitofish, Gambusia affinis. We performed morphological and histological analyses on gonads, anal fins, liver, and gills after the exposure of mosquito fish to P4. The expression levels of genes (vtg, er, and ar isoforms) related to fish reproduction and detoxification (cyp1a) in the liver were quantified by quantitative real-time polymerase chain reaction. The results showed that the progesterone exposure induced slight masculinization in female mosquitofish, influenced the oocyte maturation as revealed by histology of the ovaries, and caused severe damages to the liver and gills of adult female mosquitofish. It also suppressed the mRNAs expression of vtg, er, cyp1a, and significantly enhanced the expression of ar mRNA in the liver. This study reveals the molecular and physiological effects of progesterone at environmentally relevant concentrations, which might further be translated to alterations in the reproduction of mosquitofish. Copyright © 2017 Elsevier B.V. All rights reserved.

  5. Nicotine at clinically relevant concentrations affects atrial inward rectifier potassium current sensitive to acetylcholine.

    Bébarová, Markéta; Matejovič, Peter; Švecová, Olga; Kula, Roman; Šimurdová, Milena; Šimurda, Jiří


    Nicotine abuse is associated with variety of diseases including arrhythmias, most often atrial fibrillation (AF). Altered inward rectifier potassium currents including acetylcholine-sensitive current I K(Ach) are known to be related to AF pathogenesis. Since relevant data are missing, we aimed to investigate I K(Ach) changes at clinically relevant concentrations of nicotine. Experiments were performed by the whole cell patch clamp technique at 23 ± 1 °C on isolated rat atrial myocytes. Nicotine was applied at following concentrations: 4, 40 and 400 nM; ethanol at 20 mM (∼0.09%). Nicotine at 40 and 400 nM significantly activated constitutively active component of I K(Ach) with the maximum effect at 40 nM (an increase by ∼100%); similar effect was observed at -110 and -50 mV. Changes at 4 nM nicotine were negligible on average. Coapplication of 40 nM nicotine and 20 mM ethanol (which is also known to activate this current) did not show cumulative effect. In the case of acetylcholine-induced component of I K(Ach), a dual effect of nicotine and its correlation with the current magnitude in control were apparent: the current was increased by nicotine in the cells showing small current in control and vice versa. The effect of 40 and 400 nM nicotine on acetylcholine-induced component of I K(Ach) was significantly different at -110 and -50 mV. We conclude that nicotine at clinically relevant concentrations significantly increased constitutively active component of I K(Ach) and showed a dual effect on its acetylcholine-induced component, similarly as ethanol. Synchronous application of nicotine and ethanol did not cause additive effect.

  6. Two effects relevant for the study of astrophysical reaction rates: gamma transitions in capture reactions and Coulomb suppression of the stellar enhancement

    Rauscher, T


    Nucleosynthesis processes involve reactions on several thousand nuclei, both close to and far off stability. The preparation of reaction rates to be used in astrophysical investigations requires experimental and theoretical input. In this context, two interesting aspects are discussed: (i) the relevant gamma transition energies in astrophysical capture reactions, and (ii) the newly discovered Coulomb suppression of the stellar enhancement factor. The latter makes a number of reactions with negative Q value more favorable for experimental investigation than their inverse reactions, contrary to common belief.

  7. Environmentally Relevant Inoculum Concentrations Improve the Reliability of Persistent Assessments in Biodegradation Screening Tests.

    Martin, Timothy J; Snape, Jason R; Bartram, Abigail; Robson, Aidan; Acharya, Kishor; Davenport, Russell J


    Standard OECD biodegradation screening tests (BSTs) have not evolved at the same rate as regulatory concerns, which now place an increased emphasis on environmental persistence. Consequently, many chemicals are falsely assigned as being potentially persistent based on results from BSTs. The present study increased test duration and increased inoculum concentrations to more environmentally relevant levels to assess their impact on biodegradation outcome and intratest replicate variability for chemicals with known environmental persistence. Chemicals were assigned to potential persistence categories based on existing degradation data. These more environmentally relevant BSTs (erBSTs) improved the reliability of persistence assignment by reducing the high variability associated with these tests and the occurrence of failures at low inoculum concentrations due to the exclusion of specific degraders. Environmental fate was determined using a reference set of (14)C-labeled compounds with a range of potential environmental persistences, and full mass balance data were collated. The erBST correctly assigned five reference chemicals of known biodegradabilities to their appropriate persistence category in contrast to a standard OECD Ready Biodegradation Test (RBTs, P < 0.05). The erBST was significantly more reproducible than an OECD RBT (ANOVA, P < 0.05), with more consistent rates and extent of biodegradation observed in the erBST.

  8. The progestin levonorgestrel affects sex differentiation in zebrafish at environmentally relevant concentrations.

    Hua, Jianghuan; Han, Jian; Guo, Yongyong; Zhou, Bingsheng


    Synthetic progestins have become widespread environmental contaminants and may cause adverse effects on fish. In the present study, we investigated the effects of levonorgestrel (LNG) on sex differentiation in zebrafish (Danio rerio). Embryos were exposed to LNG at environmentally relevant concentrations (0, 1, 10, 33, and 100ng/L) and allowed to develop until sexual maturity. Histological examination at 63 days post fertilization (dpf) caused complete sex reversal and 100% males were observed in the 10, 33 and 100ng/L treatments; gross morphological and histological examination of gonads at 142dpf further confirmed 100% males at these exposure concentrations. The results indicate androgenic activity of LNG, and masculinization during zebrafish gonadal differentiation. The mRNA expression levels of genes involved in fish sex differentiation and gonadal development were examined at 28 and 42dpf. Down-regulation of the mRNA expression of aromatase (e.g., cyp19a1a, cyp19a1b), the forkhead transcription factor gene L2 (foxl2) and the Fushi tarazu factor-1d (nr5a1b) were observed. In contrast, transcription of the doublesex and mab-3-related transcription factor 1 (dmrt1) gene was up-regulated. Androgen receptor (ar) mRNA expression was significantly down-regulated at 28 and 42dpf. Co-exposure to flutamide (an androgen antagonist) and LNG, led to a decrease in the sex inversion potency of LNG. Our study has demonstrated that environmentally relevant concentrations of LNG could alter sex differentiation and gonadal development in zebrafish. Our results also suggest a potentially high ecological risk of LNG to fish populations in LNG-contaminated aquatic environments.

  9. Establishing policy relevant background (PRB) ozone concentrations in the United States.

    McDonald-Buller, Elena C; Allen, David T; Brown, Nancy; Jacob, Daniel J; Jaffe, Daniel; Kolb, Charles E; Lefohn, Allen S; Oltmans, Samuel; Parrish, David D; Yarwood, Greg; Zhang, Lin


    Policy Relevant Background (PRB) ozone concentrations are defined by the United States (U.S.) Environmental Protection Agency (EPA) as those concentrations that would occur in the U.S. in the absence of anthropogenic emissions in continental North America (i.e., the U.S, Canada, and Mexico). Estimates of PRB ozone have had an important role historically in the EPA's human health and welfare risk analyses used in establishing National Ambient Air Quality Standards (NAAQS). The margin of safety for the protection of public health in the ozone rulemaking process has been established from human health risks calculated based on PRB ozone estimates. Sensitivity analyses conducted by the EPA have illustrated that changing estimates of PRB ozone concentrations have a progressively greater impact on estimates of mortality risk as more stringent standards are considered. As defined by the EPA, PRB ozone is a model construct, but it is informed by measurements at relatively remote monitoring sites (RRMS). This review examines the current understanding of PRB ozone, based on both model predictions and measurements at RRMS, and provides recommendations for improving the definition and determination of PRB ozone.

  10. Bumblebees are not deterred by ecologically relevant concentrations of nectar toxins

    Tiedeken, Erin Jo; Stout, Jane C.; Stevenson, Philip C.; Wright, Geraldine A.


    Bees visit flowers to collect nectar and pollen that contain nutrients and simultaneously facilitate plant sexual reproduction. Paradoxically, nectar produced to attract pollinators often contains deterrent or toxic plant compounds associated with herbivore defence. The functional significance of these nectar toxins is not fully understood, but they may have a negative impact on pollinator behaviour and health, and, ultimately, plant pollination. This study investigates whether a generalist bumblebee, Bombus terrestris, can detect naturally occurring concentrations of nectar toxins. Using paired-choice experiments, we identified deterrence thresholds for five compounds found in the nectar of bee-pollinated plants: quinine, caffeine, nicotine, amygdalin and grayanotoxin. The deterrence threshold was determined when bumblebees significantly preferred a sucrose solution over a sucrose solution containing the compound. Bumblebees had the lowest deterrence threshold for the alkaloid quinine (0.01 mmol l−1); all other compounds had higher deterrence thresholds, above the natural concentration range in floral nectar. Our data, combined with previous work using honeybees, suggest that generalist bee species have poor acuity for the detection of nectar toxins. The fact that bees do not avoid nectar-relevant concentrations of these compounds likely indicates that it is difficult for them to learn to associate floral traits with the presence of toxins, thus maintaining this trait in plant populations. PMID:24526720

  11. Accelerating process and catalyst development in reforming reactions with high throughput technologies under industrially relevant conditions

    Schunk, S.A.; Bollmann, G.; Froescher, A.; Kaiser, H.; Lange de Oliveira, A.; Roussiere, T.; Wasserschaff, G. [hte Aktiengesellschaft, Heidelberg (Germany); Domke, I. [BASF SE, Ludwigshafen (Germany)


    The generation of hydrogen via reforming of a variety of carbon containing feed-stocks in the presence of water is up to date one of the most versatile technologies for the production of hydrogen and syngas. Although these reforming technologies are in principle well established, understood and commercialized, there are still a number of technological challenges that are not solved up to a satisfactorily degree and there is a constant demand for appropriate answers to the challenges posed. High throughput experimentation can be a valuable tool in helping accelerate the development of suitable solutions on the catalyst and process development side. In order to be able to generate test data that are close or identical to process relevant conditions, hte has developed a new technology portfolio of test technologies named Stage-IV technology. In contrast to earlier developments which address more small scale testing on the basis of catalyst volumes of 1ml up to 10 ml under isothermal conditions, our new technology portfolio offers the advantage of test volumes at sub-pilot scale also realizing reactor dimensions close to technical applications. This does not only ensure a good mimic of the hydrodynamic conditions of the technical scale, but also allows a fingerprinting of features like temperature gradients in the catalyst bed which play a large role for catalyst performance. Apart from catalyst tests with granulates when screening for optimized catalyst compositions, the units are designed to accommodate tests with shaped catalysts. In order to demonstrate how these technologies can accelerate catalyst and process development we have chosen technically challenging application examples: (I) Pre-reforming and reforming of methane based feeds which accelerate coking and catalyst deactivation. Higher reaction pressures, high CO{sub 2} contents in the feedgas (which occur typically in sources like bio-gas or certain types of natural gas), the presence of higher alkanes

  12. Characterization and Dynamics of Substituted Ruthenacyclobutanes Relevant to the Olefin Cross-Metathesis Reaction

    Blake, Garrett; VanderVelde, David G.; Grubbs, Robert H.


    The reaction of the phosphonium alkylidene [(H2IMes)RuCl2=CHP(Cy)3)]+ BF4– with propene, 1-butene, and 1-hexene at –45 °C affords various substituted, metathesis-active ruthenacycles. These metallacycles were found to equilibrate over extended reaction times in response to decreases in ethylene concentrations, which favored increased populations of α-monosubstituted and α,α’-disubstituted (both cis and trans) ruthenacycles. On an NMR timescale, rapid chemical exchange was found to preferentially occur between the β-hydrogens of the cis and trans stereoisomers prior to olefin exchange. Exchange on an NMR timescale was also observed between the α- and β-methylene groups of the monosubstituted ruthenacycle (H2IMes)Cl2Ru(CHRCH2CH2) (R = CH3, CH2CH3, (CH2)3CH3). EXSY NMR experiments at –87 °C were used to determine the activation energies for both of these exchange processes. In addition, new methods have been developed for the direct preparation of metathesis-active ruthenacyclobutanes via the protonolysis of dichloro(1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)(benzylidene) bis(pyridine)ruthenium(II) and its 3-bromopyridine analog. Using either trifluoroacetic acid or silica-bound toluenesulfonic acid as the proton source, the ethylene-derived ruthenacyclobutane (H2IMes)Cl2Ru(CH2CH2CH2) was observed in up to 98% yield via NMR at –40 °C. On the basis of these studies, mechanisms accounting for the positional and stereochemical exchange within ruthenacyclobutanes are proposed, as well as the implications of these dynamics towards olefin metathesis catalyst and reaction design are described. PMID:21452876

  13. Detection of Adriamycin-DNA adducts by accelerator mass spectrometry at clinically relevant Adriamycin concentrations.

    Coldwell, Kate E; Cutts, Suzanne M; Ognibene, Ted J; Henderson, Paul T; Phillips, Don R


    Limited sensitivity of existing assays has prevented investigation of whether Adriamycin-DNA adducts are involved in the anti-tumour potential of Adriamycin. Previous detection has achieved a sensitivity of a few Adriamycin-DNA adducts/10(4) bp DNA, but has required the use of supra-clinical drug concentrations. This work sought to measure Adriamycin-DNA adducts at sub-micromolar doses using accelerator mass spectrometry (AMS), a technique with origins in geochemistry for radiocarbon dating. We have used conditions previously validated (by less sensitive decay counting) to extract [(14)C]Adriamycin-DNA adducts from cells and adapted the methodology to AMS detection. Here we show the first direct evidence of Adriamycin-DNA adducts at clinically-relevant Adriamycin concentrations. [(14)C]Adriamycin treatment (25 nM) resulted in 4.4 +/- 1.0 adducts/10(7) bp ( approximately 1300 adducts/cell) in MCF-7 breast cancer cells, representing the best sensitivity and precision reported to date for the covalent binding of Adriamycin to DNA. The exceedingly sensitive nature of AMS has enabled over three orders of magnitude increased sensitivity of Adriamycin-DNA adduct detection and revealed adduct formation within an hour of drug treatment. This method has been shown to be highly reproducible for the measurement of Adriamycin-DNA adducts in tumour cells in culture and can now be applied to the detection of these adducts in human tissues.

  14. Responses of laboratory exposed catfish (Clarias gariepinus) to environmentally relevant concentrations of p,p'-DDT.

    Brink, Kerry; van Vuren, Johan; Bornman, Riana


    Technical grade DDT is annually sprayed for malaria control in many under developed countries world wide. Despite the controversy surrounding the use of DDT, minimal research concerning the effects on indigenous fish species in these areas has been conducted. In this study, the objectives were to identify some of the effects of sprayed p,p'-DDT on the common African sharptooth catfish species (Clarias gariepinus) under laboratory conditions. The effects were assessed by exposing specimens to three environmentally relevant concentrations of p,p'-DDT (0.66, 1.36 and 2.72 μg/l) for 21 days and analysing a suite of biomarkers in the plasma, gonads and body morphometrics. The biomarkers were specifically selected based on their practicality in developing countries, which could potentially be utilised for continued monitoring, and included alkali-labile phosphate (ALP), calcium, magnesium and zinc as the indirect measures of vitellogenin, gonadosomatic index, gonad mass manipulated using analysis of covariance, and condition factor. The results showed no significant (pgariepinus, indicating that these species were not responsive to the p,p'-DDT concentrations when exposed sub-chronically. This lack of a response suggested that mature C. gariepinus are tolerant to 21 days exposure of low levels of p,p'-DDT.

  15. Effects of tributyltin (TBT) on Xenopus tropicalis embryos at environmentally relevant concentrations.

    Guo, Suzhen; Qian, Lijuan; Shi, Huahong; Barry, Terence; Cao, Qinzhen; Liu, Junqi


    Tributyltin (TBT) has been widely used as a biocide in antifouling paints and is a known endocrine disrupting chemical. In this paper, we exposed embryos of Xenopus tropicalis to 50-400ngL(-1) tributyltin chloride. TBT significantly decreased the survival rate, reduced the body length and retarded the development of embryos after 24, 36 and 48h of exposure. These effects of TBT were concentration- and time-dependent. Embryos treated with TBT showed multiple malformations. The most obvious alterations were abnormal eyes, enlarged proctodaeum, narrow fins, and skin hypopigmentation. Enlarged proctodaeum and narrow fins were mainly observed after 36 and 48h of exposure. The loss of eye pigmentation or the absence of external eyes occurred after 24 and 36h of exposure, while extended lenses or edemas of eyes were more commonly observed after 48h of exposure. Additional malformations included: small anterior region of heads, pericardial edemas, enlarged trunks, and bent tails. These results suggested that TBT is very toxic to X. tropicalis embryos at environmentally relevant concentrations.

  16. Transformer fault diagnosis based on chemical reaction optimization algorithm and relevance vector machine

    Luo Wei


    Full Text Available Power transformer is one of the most important equipment in power system. In order to predict the potential fault of power transformer and identify the fault types correctly, we proposed a transformer fault intelligent diagnosis model based on chemical reaction optimization (CRO algorithm and relevance vector machine(RVM. RVM is a powerful machine learning method, which can solve nonlinear, high-dimensional classification problems with a limited number of samples. CRO algorithm has well global optimization and simple calculation, so it is suitable to solve parameter optimization problems. In this paper, firstly, a multi-layer RVM classification model was built by binary tree recognition strategy. Secondly, CRO algorithm was adopted to optimize the kernel function parameters which could enhance the performance of RVM classifiers. Compared with IEC three-ratio method and the RVM model, the CRO-RVM model not only overcomes the coding defect problem of IEC three-ratio method, but also has higher classification accuracy than the RVM model. Finally, the new method was applied to analyze a transformer fault case, Its predicted result accord well with the real situation. The research provides a practical method for transformer fault intelligent diagnosis and prediction.

  17. Extent-based incremental identification of reaction systems using concentration and calorimetric measurements

    Srinivasan, Sriniketh; Bhatt, Nirav Pravinbhai; Billeter, Julien; Bonvin, Dominique


    Extent-based Incremental Model Identification (IMI) uses the concept of extent of reaction and the integral method of parameter estimation to identify reaction kinetics from transient concentration measurements. This study proposes to incorporate calorimetric measurements into the extent-based IMI approach. Calorimetric measurements are added to concentrationmeasurements for two main purposes: (i) to be able to estimate the reaction enthalpies when all the concentrations are measured, and (ii...

  18. Kinetics of the decomposition reaction of phosphorite concentrate

    Huang Run


    Full Text Available Apatite is the raw material, which is mainly used in phosphate fertilizer, and part are used in yellow phosphorus, red phosphorus, and phosphoric acid in the industry. With the decrease of the high grade phosphorite lump, the agglomeration process is necessary for the phosphorite concentrate after beneficiation process. The decomposition behavior and the phase transformation are of vital importance for the agglomeration process of phosphorite. In this study, the thermal kinetic analysis method was used to study the kinetics of the decomposition of phosphorite concentrate. The phosphorite concentrate was heated under various heating rate, and the phases in the sample heated were examined by the X-ray diffraction method. It was found that the main phases in the phosphorite are fluorapatiteCa5(PO43F, quartz SiO2,and dolomite CaMg(CO32.The endothermic DSC peak corresponding to the mass loss caused by the decomposition of dolomite covers from 600°C to 850°C. The activation energy of the decomposition of dolomite, which increases with the increase in the extent of conversion, is about 71.6~123.6kJ/mol. The mechanism equation for the decomposition of dolomite agrees with the Valensi equation and G-B equation.

  19. Ketoconazole inhibits the cellular uptake of anandamide via inhibition of FAAH at pharmacologically relevant concentrations.

    Emmelie Björklund

    Full Text Available BACKGROUND: The antifungal compound ketoconazole has, in addition to its ability to interfere with fungal ergosterol synthesis, effects upon other enzymes including human CYP3A4, CYP17, lipoxygenase and thromboxane synthetase. In the present study, we have investigated whether ketoconazole affects the cellular uptake and hydrolysis of the endogenous cannabinoid receptor ligand anandamide (AEA. METHODOLOGY/PRINCIPAL FINDINGS: The effects of ketoconazole upon endocannabinoid uptake were investigated using HepG2, CaCo2, PC-3 and C6 cell lines. Fatty acid amide hydrolase (FAAH activity was measured in HepG2 cell lysates and in intact C6 cells. Ketoconazole inhibited the uptake of AEA by HepG2 cells and CaCo2 cells with IC50 values of 17 and 18 µM, respectively. In contrast, it had modest effects upon AEA uptake in PC-3 cells, which have a low expression of FAAH. In cell-free HepG2 lysates, ketoconazole inhibited FAAH activity with an IC50 value (for the inhibitable component of 34 µM. CONCLUSIONS/SIGNIFICANCE: The present study indicates that ketoconazole can inhibit the cellular uptake of AEA at pharmacologically relevant concentrations, primarily due to its effects upon FAAH. Ketoconazole may be useful as a template for the design of dual-action FAAH/CYP17 inhibitors as a novel strategy for the treatment of prostate cancer.

  20. Physiological response of the epiphytic lichen Evernia prunastri (L.) Ach. to ecologically relevant nitrogen concentrations.

    Munzi, S; Paoli, L; Fiorini, E; Loppi, S


    This study investigated the physiological response of the epiphytic lichen Evernia prunastri to ecologically relevant concentrations of nitrogen compounds. Lichen samples were sprayed for 4 weeks either with water or 50, 150 and 500 μM NH(4)Cl. The integrity of cell membranes and chlorophyll a fluorescence emission (F(V)/F(M) and PI(ABS)) were analyzed. No membrane damage occurred after the exposure period. F(V)/F(M), a classical fluorescence indicator, decreased during the second week of treatment with 500 μM NH(4)Cl and the third week with 50 and 150 μM NH(4)Cl. PI(ABS), an overall index of the photosynthetic performance, was more sensitive and decreased already during the first week with 500 μM NH(4)Cl and the second week with 150 μM NH(4)Cl. Since E. prunastri has been exposed to ammonium loads corresponding to real environmental conditions, these findings open the way to an effective use of this species as early indicators of environmental nitrogen excess. Copyright © 2012 Elsevier Ltd. All rights reserved.

  1. Multiphase fluid-rock reactions among supercritical carbon dioxide, brine, aquifer, and caprock: relevance to geologic sequestration of carbon

    Kaszuba, J. P. (John P.); Janecky, D. R. (David R.); Snow, M. G. (Marjorie G.)


    The reactive behavior of a multiphase fluid (supercritical CO{sub 2} and brine) under physical-chemical conditions relevant to geologic storage and sequestration in a carbon repository is largely unknown. Experiments were conducted in a flexible cell hydrothermal apparatus to evaluate multiphase fluid-rock (aquifer plus caprock) reactions that may impact repository integrity.

  2. Sublethal effects on wood frogs chronically exposed to environmentally relevant concentrations of two neonicotinoid insecticides.

    Robinson, Stacey A; Richardson, Sarah D; Dalton, Rebecca L; Maisonneuve, France; Trudeau, Vance L; Pauli, Bruce D; Lee-Jenkins, Stacey S Y


    Neonicotinoids are prophylactically used globally on a variety of crops, and there is concern for the potential impacts of neonicotinoids on aquatic ecosystems. The intensive use of pesticides on crops has been identified as a contributor to population declines of amphibians, but currently little is known regarding the sublethal effects of chronic neonicotinoid exposure on amphibians. The objective of the present study was to characterize the sublethal effect(s) of exposure to 3 environmentally relevant concentrations (1 μg/L, 10 μg/L, and 100 μg/L) of 2 neonicotinoids on larval wood frogs (Lithobates sylvaticus) using outdoor mesocosms. We exposed tadpoles to solutions of 2 commercial formulations containing imidacloprid and thiamethoxam, and assessed survival, growth, and development. Exposure to imidacloprid at 10 μg/L and 100 μg/L increased survival and delayed completion of metamorphosis compared with controls. Exposure to thiamethoxam did not influence amphibian responses. There was no significant effect of any treatment on body mass or size of the metamorphs. The results suggest that current usage of imidacloprid and thiamethoxam does not pose a threat to wood frogs. However, further assessment of both direct and indirect effects on subtle sublethal endpoints, and the influence of multiple interacting stressors at various life stages, is needed to fully understand the effects of neonicotinoids on amphibians. Environ Toxicol Chem 2017;36:1101-1109. © 2017 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals, Inc. on behalf of SETAC. © 2017 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals, Inc. on behalf of SETAC.

  3. Physiologically relevant plasma d,l-homocysteine concentrations mobilize Cd from human serum albumin.

    Sagmeister, Peter; Gibson, Matthew A; McDade, Kyle H; Gailer, Jürgen


    Although low-level chronic exposure of humans to cadmium (Cd(2+)) can result in a variety of adverse health effects, little is known about the role that its interactions with plasma proteins and small molecular weight (SMW) ligands in the bloodstream may play in delivering this metal to its target organs. To gain insight, a Cd-human serum albumin (HSA) 1:1 (molar ratio) complex was analyzed by size exclusion chromatography (SEC) coupled on-line to a flame atomic absorption spectrometer (FAAS). Using a phosphate buffered saline (PBS)-buffer mobile phase, the stability of the Cd-HSA complex was investigated in the presence of 2.0mM of SMW ligands, including taurine, acetaminophen, l-methionine, l-cysteine (Cys), d,l-homocysteine (hCys) or l-cysteine methyl-ester (Cys-Me). While taurine, acetaminophen and l-methionine did not affect its integrity, Cys, hCys and Cys-Me completely abstracted Cd from HSA. Subsequent investigations into the effect of 1.5, 1.0 and 0.5mM Cys and hCys on the integrity of the Cd-HSA complex revealed clear differences with regard to the nature of the eluting SMW-Cd species between these structurally related endogenous thiols. Interestingly, the Cd-specific chromatograms that were obtained for 0.5mM hCys revealed the elution of an apparent mixture of the parent Cd-HSA complex with a significant contribution of a structurally uncharacterized CdxhCysy species. Since this hCys concentration is encountered in blood plasma of hyperhomocysteinemia patients and since previous studies by others have revealed that a SH-containing carrier mediates the uptake of Cd into hepatocytes, our results suggest that plasma hCys may play a role in the toxicologically relevant translocation of Cd from the bloodstream to mammalian target organs.

  4. Theoretical studies of nonadiabatic and spin-forbidden processes: Investigations of the reactions and spectroscopy of radical species relevant to combustion reactions and diagnostics

    Yarkony, D.R. [Johns Hopkins Univ., Baltimore, MD (United States)


    This research program focusses on studies of spin-forbidden and electronically nonadiabatic processes involving radical species relevant to combustion reactions and combustion diagnostics. To study the electronic structure aspects of these processes a unique and powerful system of electronic structure programs, developed over the past nine years, the BROOKLYN codes, is employed. These programs enable the authors to address questions basic to the understanding of elementary combustion processes not tractable using more standard quantum chemistry codes.

  5. Catalytic conversion reactions in nanoporous systems with concentration-dependent selectivity: Statistical mechanical modeling

    García, Andrés; Wang, Jing; Windus, Theresa L.; Sadow, Aaron D.; Evans, James W.


    Statistical mechanical modeling is developed to describe a catalytic conversion reaction A →Bc or Bt with concentration-dependent selectivity of the products, Bc or Bt, where reaction occurs inside catalytic particles traversed by narrow linear nanopores. The associated restricted diffusive transport, which in the extreme case is described by single-file diffusion, naturally induces strong concentration gradients. Furthermore, by comparing kinetic Monte Carlo simulation results with analytic treatments, selectivity is shown to be impacted by strong spatial correlations induced by restricted diffusivity in the presence of reaction and also by a subtle clustering of reactants, A .

  6. Low-temperature Kinetic Studies of OH Radical Reactions Relevant to Planetary Atmospheres

    Townsend, T. M.; Antiñolo, M.; Ballesteros, B.; Jimenez, E.; Canosa, A.


    In the solar system, the temperature (T) of the atmosphere of giant planets or their satellites is only several tens of Kelvin (K). The temperature of the tropopause of Titan (satellite of Saturn) and the surface of Mars is 70 K and 210 K, respectively. In the Earth's atmosphere, T decreases from 298 K (surface) to 210 K close to the T-inversion region (tropopause). The principal oxidants in the Earth's lower atmosphere are ozone, the hydroxyl (OH) radical and hydrogen peroxide. A number of critical atmospheric chemical problems depend on the Earth's oxidising capacity, which is essentially the global burden of these oxidants. In the interstellar clouds and circumstellar envelopes, OH radicals have also been detected. As the chemistry of atmospheres is highly influenced by temperature, the knowledge of the T-dependence of the rate coefficients for OH-reactions (k) is the key to understanding the underlying molecular mechanisms. In general, these reactions take place on a short temporal scale. Therefore, a detection technique with high temporal resolution is required. Measurements of k at low temperatures can be achieved by maintaining a thermalised environment using either cryogenic cooling (T>200 K) or supersonic gas expansion with a Laval nozzle (several tens of K). The pulsed laser photolysis technique coupled with laser induced fluorescence detection has been widely used in our laboratory to determine the rate coefficients of OH-reactions with different volatile organic compounds, such as alcohols (1), saturated and unsaturated aliphatic aldehydes (2), linear ketones (3), as a function of temperature (260 350 K). An experimental system based on the CRESU (Cinetique de Reaction en Ecoulement Supersonique Uniforme or Reaction Kinetics in a Uniform Supersonic Flow) technique is currently under construction. This technique will allow the performance of kinetic studies of OH-reactions of astrophysical interest at temperatures lower than 200 K.

  7. Genome-wide mapping for clinically relevant predictors of lamotrigine- and phenytoin-induced hypersensitivity reactions.

    McCormack, Mark


    An association between carbamazepine-induced hypersensitivity and HLA-A*3101 has been reported in populations of both European and Asian descent. We aimed to investigate HLA-A*3101 and other common variants across the genome as markers for cutaneous adverse drug reactions (cADRs) attributed to lamotrigine and phenytoin.

  8. The 23Na({\\alpha},p) 26Mg reaction rate at astrophysically relevant energies

    Howard, A M; Fynbo, H O U; Kirsebom, O S; Laursen, K L; Diget, C Aa; Hubbard, N J


    The production of 26 Al in massive stars is sensitive to the 23 Na(a,p) 26 Mg cross section. Recent experimental data suggest the currently recommended cross sections are underestimated by a factor of 40. We present here differential cross sections for the 23 Na(a,p) 26 Mg reaction measured in the energy range E c.m. = 1.7 - 2.5 MeV. Concurrent measurements of Rutherford scattering provide absolute normalisations which are independent of variations in target properties. Angular distributions were measured for both p 0 and p 1 permitting the determination of total cross sections. The results show no significant deviation from the statistical model calculations upon which the recommended rates are based. We therefore retain the previous recommendation without the increase in cross section and resulting stellar reaction rates of a factor of 40, impacting on the 26 Al yield from massive stars by more than a factor of three.

  9. A review of the electrophilic reaction chemistry involved in covalent protein binding relevant to toxicity.

    Enoch, S J; Ellison, C M; Schultz, T W; Cronin, M T D


    Several pieces of legislation have led to an increased interest in the use of in silico methods, specifically the formation of chemical categories for the assessment of toxicological endpoints. For a number of endpoints, this requires a detailed knowledge of the electrophilic reaction chemistry that governs the ability of an exogenous chemical to form a covalent adduct. Historically, this chemistry has been defined as compilations of structural alerts without documenting the associated electrophilic chemistry mechanisms. To address this, this article has reviewed the literature defining the structural alerts associated with covalent protein binding and detailed the associated electrophilic reaction chemistry. This information is useful to both toxicologists and regulators when using the chemical category approach to fill data gaps for endpoints involving covalent protein binding. The structural alerts and associated electrophilic reaction chemistry outlined in this review have been incorporated into the OECD (Q)SAR Toolbox, a freely available software tool designed to fill data gaps in a regulatory environment without the need for further animal testing.

  10. Development of an inertial confinement fusion platform to study charged-particle-producing nuclear reactions relevant to nuclear astrophysics

    Gatu Johnson, M.; Zylstra, A. B.; Bacher, A.; Brune, C. R.; Casey, D. T.; Forrest, C.; Herrmann, H. W.; Hohenberger, M.; Sayre, D. B.; Bionta, R. M.; Bourgade, J.-L.; Caggiano, J. A.; Cerjan, C.; Craxton, R. S.; Dearborn, D.; Farrell, M.; Frenje, J. A.; Garcia, E. M.; Glebov, V. Yu.; Hale, G.; Hartouni, E. P.; Hatarik, R.; Hohensee, M.; Holunga, D. M.; Hoppe, M.; Janezic, R.; Khan, S. F.; Kilkenny, J. D.; Kim, Y. H.; Knauer, J. P.; Kohut, T. R.; Lahmann, B.; Landoas, O.; Li, C. K.; Marshall, F. J.; Masse, L.; McEvoy, A.; McKenty, P.; McNabb, D. P.; Nikroo, A.; Parham, T. G.; Paris, M.; Petrasso, R. D.; Pino, J.; Radha, P. B.; Remington, B.; Rinderknecht, H. G.; Robey, H.; Rosenberg, M. J.; Rosse, B.; Rubery, M.; Sangster, T. C.; Sanchez, J.; Schmitt, M.; Schoff, M.; Séguin, F. H.; Seka, W.; Sio, H.; Stoeckl, C.; Tipton, R. E.


    This paper describes the development of a platform to study astrophysically relevant nuclear reactions using inertial-confinement fusion implosions on the OMEGA and National Ignition Facility laser facilities, with a particular focus on optimizing the implosions to study charged-particle-producing reactions. Primary requirements on the platform are high yield, for high statistics in the fusion product measurements, combined with low areal density, to allow the charged fusion products to escape. This is optimally achieved with direct-drive exploding pusher implosions using thin-glass-shell capsules. Mitigation strategies to eliminate a possible target sheath potential which would accelerate the emitted ions are discussed. The potential impact of kinetic effects on the implosions is also considered. The platform is initially employed to study the complementary T(t,2n)α, T(3He,np)α and 3He(3He,2p)α reactions. Proof-of-principle results from the first experiments demonstrating the ability to accurately measure the energy and yields of charged particles are presented. Lessons learned from these experiments will be used in studies of other reactions. The goals are to explore thermonuclear reaction rates and fundamental nuclear physics in stellar-like plasma environments, and to push this new frontier of nuclear astrophysics into unique regimes not reachable through existing platforms, with thermal ion velocity distributions, plasma screening, and low reactant energies.

  11. Chronic ZnO-NPs exposure at environmentally relevant concentrations results in metabolic and locomotive toxicities in Caenorhabditis elegans.

    Huang, Chi-Wei; Li, Shang-Wei; Hsiu-Chuan Liao, Vivian


    ZnO nanoparticles (ZnO-NPs) are emerging contaminants that raise the concerns of potential risk in the aquatic environment. It has been estimated that the environmental ZnO-NPs concentration is 76 μg/l in the aquatic environment. Our aim was to determine the aquatic toxicity of ZnO-NPs with chronic exposure at environmentally relevant concentrations using the nematode Caenorhabditis elegans. Two simulated environmentally relevant mediums-moderately hard reconstituted water (EPA water) and simulated soil pore water (SSPW)-were used to represent surface water and pore water in sediment, respectively. The results showed that the ZnO-NPs in EPA water has a much smaller hydrodynamic diameter than that in SSPW. Although the ionic release of Zn ions increased time-dependently in both mediums, the Zn ions concentrations in EPA water increased two-fold more than that in SSPW at 48 h and 72 h. The ZnO-NPs did not induce growth defects or decrease head thrashes in C. elegans in either media. However, chronic exposure to ZnO-NPs caused a significant reduction in C. elegans body bends in EPA water even with a relatively low concentration (0.05 μg/l); similar results were not observed in SSPW. Moreover, at the same concentrations (50 and 500 μg/l), body bends in C. elegans were reduced more severely in ZnO-NPs than in ZnCl2 in EPA water. The ATP levels were consistently and significantly decreased, and ROS was induced after ZnO-NPs exposure (50 and 500 μg/l) in EPA water. Our results provide evidences that chronic exposure to ZnO-NPs under environmentally relevant concentrations causes metabolic and locomotive toxicities implicating the potential ecotoxicity of ZnO-NPs at low concentrations in aquatic environments.

  12. Review: Drug concentrations in hair and their relevance in drug facilitated crimes.

    Xiang, Ping; Shen, Min; Drummer, Olaf H


    Segmental hair analysis can provide valuable retrospective information on the history of drug exposure in victims of drug facilitated crimes (DFC). This is now possible with availability of sensitive tandem MS techniques such as GC-MS/MS and LC-MS/MS allowing drugs to be detected at pg/mg concentrations after a single dose. In this review hair concentrations of 35 psychoactive drugs given in 20 controlled dose studies are reviewed and compared to the 25 different drugs detected in reported case work. The most common drugs were the benzodiazepines and related hypnotics, gamma-hydroxybutyrate (GHB), ketamine and methamphetamine. Those concentrations reported in DFC were mostly similar or higher than that seen in controlled dose studies. The factors that affecting interpretation of segmental hair results including hair color, growth rates, sample preparation and surface contamination are discussed.

  13. Laboratory simulation of SO2 heterogeneous reactions on hematite surface under different SO2 concentrations

    CUI Huxiong; CHENG Tiantao; YU Xingna; CHEN Jianmin; XU Yongfu; FANG Wen


    The variations of sulfate formation and optical coefficients during SO2 heterogeneous reactions on hematite surface under different SO2 concentrations were examined using in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and ion chromatograph (IC). Laboratory experiments revealed that within ambient SO2 of 0.51--18.6 ppmv, sulfate product, producing velocity, absorption and backward scattering coefficients showed an increasing trend with SO2 concentration. Under given SO2 concentration, the velocity of sulfate producing performed an evolution of initial increasing, midterm decreasing and final stabilizing. The reactive uptake and Brunauer-Emmett-Teller (BET) uptake coefficients of heterogeneous reactions rose with SO2 and exhibited high reactivities. Considering global warming, this result is important for the knowledge of heterogeneous reactions of SO2 on mineral particle surface in the atmosphere and the assessment of their impacts on radiative forcing.

  14. Effects of acid concentration on intramolecular charge transfer reaction of 4-(azetidinyl) benzonitrile in solution

    Biswajit Guchhait; Tuhin Pradhan; Ranjit Biswas


    Effects of acid concentration on excited state intramolecular charge transfer reaction of 4-(azetidinyl) benzonitrile (P4C) in aprotic (acetonitrile and ethyl acetate) and protic (ethanol) solvents have been studied by means of steady state absorption and fluorescence, and time resolved fluorescence spectroscopic techniques. While absorption and fluorescence bands of P4C have been found to be shifted towards higher energy with increasing acid concentration in acetonitrile and ethyl acetate, no significant dependence has been observed in ethanolic solutions. Reaction rate becomes increasingly slower with acid concentration in acetonitrile and ethyl acetate. In contrast, acid in ethanolic solutions does not produce such an effect on reaction rate. Time-dependent density functional theory calculations have been performed to understand the observed spectroscopic results.

  15. Capture reactions at astrophysically relevant energies: extended gas target experiments and GEANT simulations

    Kölle, V; Braitmayer, S E; Mohr, P J; Wilmes, S; Staudt, G; Hammer, J W; Jäger, M; Knee, H; Kunz, R; Mayer, A


    Several resonances of the capture reaction sup 2 sup 0 Ne(alpha, gamma) sup 2 sup 4 Mg were measured using an extended windowless gas target system. Detailed GEANT simulations were performed to derive the strength and the total width of the resonances from the measured yield curve. The crucial experimental parameters, which are mainly the density profile in the gas target and the efficiency of the gamma-ray detector, were analyzed by a comparison between the measured data and the corresponding simulation calculations. The excellent agreement between the experimental data and the simulations gives detailed insight into these parameters. (author)

  16. Clinical relevance of plasma prostaglandin F2α metabolite concentrations in patients with idiopathic pulmonary fibrosis.

    Kensaku Aihara

    Full Text Available BACKGROUND: Idiopathic pulmonary fibrosis (IPF is a devastating lung disease of unknown etiology with few current treatment options. Recently, we determined an important role of prostaglandin F2α (PGF2α in pulmonary fibrosis by using a bleomycin-induced pulmonary fibrosis model and found an abundance of PGF2α in bronchoalveolar lavage fluid of IPF patients. We investigated the role of PGF2α in human IPF by assessing plasma concentrations of 15-keto-dihydro PGF2α, a stable metabolite of PGF2α. METHODS: We measured plasma concentrations of 15-keto-dihydro PGF2α in 91 IPF patients and compared these values with those of controls (n = 25. We further investigated the relationships of plasma 15-keto-dihydro PGF2α concentrations with disease severity and mortality. RESULTS: Plasma concentrations of 15-keto-dihydro PGF2α were significantly higher in IPF patients than controls (p<0.001. Plasma concentrations of this metabolite were significantly correlated with forced expiratory volume in 1 second (Rs [correlation coefficient] = -0.34, p = 0.004, forced vital capacity (Rs = -0.33, p = 0.005, diffusing capacity for carbon monoxide (Rs = -0.36, p = 0.003, the composite physiologic index (Rs = 0.40, p = 0.001, 6-minute walk distance (Rs = -0.24, p = 0.04 and end-exercise oxygen saturation (Rs = -0.25, p = 0.04 when patients with emphysema were excluded. Multivariate analysis using stepwise Cox proportional hazards model showed that a higher composite physiologic index (relative risk = 1.049, p = 0.002 and plasma 15-keto-dihydro PGF2α concentrations (relative risk = 1.005, p = 0.002 were independently associated with an increased risk of mortality. CONCLUSIONS: We demonstrated significant associations of plasma concentrations of PGF2α metabolites with disease severity and prognosis, which support a potential pathogenic role for PGF2α in human IPF.

  17. Estradiol and endocrine disrupting compounds adversely affect development of sea urchin embryos at environmentally relevant concentrations.

    Roepke, Troy A; Snyder, Mark J; Cherr, Gary N


    Environmental endocrine disrupting compounds (EDCs) are a wide variety of chemicals that typically exert effects, either directly or indirectly, through receptor-mediated processes, thus mimicking endogenous hormones and/or inhibiting normal hormone activities and metabolism. Little is known about the effects of EDCs on echinoderm physiology, reproduction and development. We exposed developing sea urchin embryos (Strongylocentrotus purpuratus and Lytechinus anamesus) to two known EDCs (4-octylphenol (OCT), bisphenol A (BisA)) and to natural and synthetic reproductive hormones (17beta-estradiol (E2), estrone (E1), estriol (E3), progesterone (P4) and 17alpha-ethynylestradiol (EE2)). In addition, we studied two non-estrogenic EDCs, tributyltin (TBT) and o,p-DDD. Successful development to the pluteus larval stage (96 h post-fertilization) was used to define EDC concentration-response relationships. The order of compound potency based on EC50 values for a reduction in normal development was as follows: TBT(L. anamesus)>OCT>TBT(S. purpuratus)>E2>EE2>DDD>BisA>P4>E1>E3. The effect of TBT was pronounced even at concentrations substantially lower than those commonly reported in heavily contaminated areas, but the response was significantly different in the two model species. Sea urchin embryos were generally more sensitive to estrogenic EDCs and TBT than most other invertebrate larvae. Stage-specific exposure experiments were conducted to determine the most sensitive developmental periods using blastula, gastrula and post-gastrula (pluteus) stages. The stage most sensitive to E2, OCT and TBT was the blastula stage with less overall sensitivity in the gastrula stage, regardless of concentration. Selective estrogen receptor modulators (SERMs) were added to the experiments individually and in combination with estrogenic EDCs to interfere with potential receptor-mediated actions. Tamoxifen, a partial ER agonist, alone inhibited development at concentrations as low as 0.02 ng

  18. Developing mononuclear copper-active-oxygen complexes relevant to reactive intermediates of biological oxidation reactions.

    Itoh, Shinobu


    Active-oxygen species generated on a copper complex play vital roles in several biological and chemical oxidation reactions. Recent attention has been focused on the reactive intermediates generated at the mononuclear copper active sites of copper monooxygenases such as dopamine β-monooxygenase (DβM), tyramine β-monooxygenase (TβM), peptidylglycine-α-hydroxylating monooxygenase (PHM), and polysaccharide monooxygenases (PMO). In a simple model system, reaction of O2 and a reduced copper(I) complex affords a mononuclear copper(II)-superoxide complex or a copper(III)-peroxide complex, and subsequent H(•) or e(-)/H(+) transfer, which gives a copper(II)-hydroperoxide complex. A more reactive species such as a copper(II)-oxyl radical type species could be generated via O-O bond cleavage of the peroxide complex. However, little had been explored about the chemical properties and reactivity of the mononuclear copper-active-oxygen complexes due to the lack of appropriate model compounds. Thus, a great deal of effort has recently been made to develop efficient ligands that can stabilize such reactive active-oxygen complexes in synthetic modeling studies. In this Account, I describe our recent achievements of the development of a mononuclear copper(II)-(end-on)superoxide complex using a simple tridentate ligand consisting of an eight-membered cyclic diamine with a pyridylethyl donor group. The superoxide complex exhibits a similar structure (four-coordinate tetrahedral geometry) and reactivity (aliphatic hydroxylation) to those of a proposed reactive intermediate of copper monooxygenases. Systematic studies based on the crystal structures of copper(I) and copper(II) complexes of the related tridentate supporting ligands have indicated that the rigid eight-membered cyclic diamine framework is crucial for controlling the geometry and the redox potential, which are prerequisites for the generation of such a unique mononuclear copper(II)-(end-on)superoxide complex

  19. Stereoselective differentiation in the Salt-induced Peptide Formation reaction and its relevance for the origin of life.

    Plankensteiner, Kristof; Reiner, Hannes; Rode, Bernd M


    All living organisms on earth are almost totally made up of biomolecules of only one chiral form. For example, proteins are built almost exclusively of L-amino acids, and sugars are composed of D-saccharides, a fact that is usually referred to as biohomochirality. Its origin is the center of numerous investigations and theories but is not really elucidated yet. The results of experimental investigations of peptide formation in a prebiotically relevant scenario, as described in this paper, give indications on a possible pathway for the synthesis of homochiral L-peptides in the course of the Salt-induced Peptide Formation (SIPF) reaction.

  20. The relevant research on AOD and concentration of PM2.5 pollutant

    Yao, Huan; Ni, Xiaochang; Wang, Xuan; Li, Tong; Xu, Lijuan; Song, Zhenming


    To study the relationship between Aerosol Optical Depth (AOD) and concentration of PM2.5 - Particulate Matter) basing on CALIPSO (Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observation) data, 51 samples among the CALIPSO Level 2 aerosol profile data of local region from January to April 2014 are selected. After screening these 51 samples under the decided conditions, such as system stability and the type of the materials, the AODs of the samples are calculated. Then a linear regression model is constructed through Matlab software, in which AOD is independent variable and PM2.5 is dependent variable. All the data are fit by the selected five functions: linear, logarithmic, exponential, power, and quadratic. Experimental results show that the value of correlation coefficient of the quadratic equation model is the best one among the functions. So it is feasible to monitor the concentration of PM2.5 using the AOD calculated from CALIPSO Level 2 data.

  1. Transcriptional Response of the Archaeal Ammonia Oxidizer Nitrosopumilus maritimus to Low and Environmentally Relevant Ammonia Concentrations

    Nakagawa, Tatsunori; Stahl, David A.


    The ability of chemoautotrophic ammonia-oxidizing archaea to compete for ammonia among marine microorganisms at low ambient concentrations has been in part attributed to their extremely high affinity for ammonia, but as yet there is no mechanistic understanding of supporting metabolism. We examined transcription of selected genes for anabolic functions (CO2 fixation, ammonia transport, and cell wall synthesis) and a central catabolic function (ammonia oxidation) in the thaumarchaeon Nitrosopu...

  2. Shear-induced reaction-limited aggregation kinetics of brownian particles at arbitrary concentrations.

    Zaccone, Alessio; Gentili, Daniele; Wu, Hua; Morbidelli, Massimo


    The aggregation of interacting brownian particles in sheared concentrated suspensions is an important issue in colloid and soft matter science per se. Also, it serves as a model to understand biochemical reactions occurring in vivo where both crowding and shear play an important role. We present an effective medium approach within the Smoluchowski equation with shear which allows one to calculate the encounter kinetics through a potential barrier under shear at arbitrary colloid concentrations. Experiments on a model colloidal system in simple shear flow support the validity of the model in the concentration range considered. By generalizing Kramers' rate theory to the presence of shear and collective hydrodynamics, our model explains the significant increase in the shear-induced reaction-limited aggregation kinetics upon increasing the colloid concentration.

  3. Estradiol and endocrine disrupting compounds adversely affect development of sea urchin embryos at environmentally relevant concentrations

    Roepke, Troy A. [Bodega Marine Laboratory, University of California, Davis, POB 247, Bodega Bay, CA 94923 (United States); Snyder, Mark J. [Bodega Marine Laboratory, University of California, Davis, POB 247, Bodega Bay, CA 94923 (United States); Cherr, Gary N. [Bodega Marine Laboratory, University of California, Davis, POB 247, Bodega Bay, CA 94923 (United States) and Departments of Environmental Toxicology and Nutrition, One Shields Avenue, University of California, Davis, CA 95616 (United States)]. E-mail:


    Environmental endocrine disrupting compounds (EDCs) are a wide variety of chemicals that typically exert effects, either directly or indirectly, through receptor-mediated processes, thus mimicking endogenous hormones and/or inhibiting normal hormone activities and metabolism. Little is known about the effects of EDCs on echinoderm physiology, reproduction and development. We exposed developing sea urchin embryos (Strongylocentrotus purpuratus and Lytechinus anamesus) to two known EDCs (4-octylphenol (OCT), bisphenol A (BisA)) and to natural and synthetic reproductive hormones (17{beta}-estradiol (E{sub 2}), estrone (E{sub 1}), estriol (E{sub 3}), progesterone (P{sub 4}) and 17{alpha}-ethynylestradiol (EE{sub 2})). In addition, we studied two non-estrogenic EDCs, tributyltin (TBT) and o,p-DDD. Successful development to the pluteus larval stage (96 h post-fertilization) was used to define EDC concentration-response relationships. The order of compound potency based on EC{sub 50} values for a reduction in normal development was as follows: TBT {sub L.anamesus} > OCT > TBT {sub S.{sub p}}{sub urpuratus} >> E{sub 2} > EE{sub 2} > DDD >> BisA > P{sub 4} > E{sub 1} >> E{sub 3}. The effect of TBT was pronounced even at concentrations substantially lower than those commonly reported in heavily contaminated areas, but the response was significantly different in the two model species. Sea urchin embryos were generally more sensitive to estrogenic EDCs and TBT than most other invertebrate larvae. Stage-specific exposure experiments were conducted to determine the most sensitive developmental periods using blastula, gastrula and post-gastrula (pluteus) stages. The stage most sensitive to E{sub 2}, OCT and TBT was the blastula stage with less overall sensitivity in the gastrula stage, regardless of concentration. Selective estrogen receptor modulators (SERMs) were added to the experiments individually and in combination with estrogenic EDCs to interfere with potential receptor

  4. Transcriptional response of the archaeal ammonia oxidizer Nitrosopumilus maritimus to low and environmentally relevant ammonia concentrations.

    Nakagawa, Tatsunori; Stahl, David A


    The ability of chemoautotrophic ammonia-oxidizing archaea to compete for ammonia among marine microorganisms at low ambient concentrations has been in part attributed to their extremely high affinity for ammonia, but as yet there is no mechanistic understanding of supporting metabolism. We examined transcription of selected genes for anabolic functions (CO2 fixation, ammonia transport, and cell wall synthesis) and a central catabolic function (ammonia oxidation) in the thaumarchaeon Nitrosopumilus maritimus SCM1 growing at two ammonia concentrations, as measured by combined ammonia and ammonium, one well above the Km for ammonia oxidation (∼500 μM) and the other well below the Km (ammonia-replete to ammonia-limiting conditions. Transcript levels for ammonia oxidation, CO2 fixation, and one of the ammonia transport genes were approximately the same at high and low ammonia availability. Transcripts for all analyzed genes decreased with time in the complete absence of ammonia, but with various rates of decay. The new steady-state mRNA levels established are presumably more reflective of the natural physiological state of ammonia-oxidizing archaea and offer a reference for interpreting message abundance patterns in the natural environment.

  5. Neutron-induced reactions relevant for Inertial-Cofinement Fusion Experiments

    Boswell, Melissa; Merrill, Frank; Rundberg, R.; Grim, Gary; Wilde, Carl; Hayes, Anna; Fowler, Malcom; Wilhelmy, Jerry


    Measuring the fluencies of both the low- & high-energy neutrons is a powerful mechanism for studying the implosion process, and the various parameters that drive inertial confinement fusion. We have developed a number of tools to measure the spectral characteristics of the NIF neutron spectrum. Most of these methods rely on exploiting the energy dependence of (n,γ), (n,2n), (n,3n) and (n,p) reactions on a variety of materials either implicitly present in the NIF implosion or through doping the target capsule or holraum. I will be discussing both prompt activation measurements, and debris activation measurements of these materials currently under development at LANL. Focusing specifically on the development of an in-situ detector to measure short-lived activation products, as well as a low-background counting facility we are developing at the Waste Isolation Pilot Plant (WIPP) to study longer-lived activation products. Furthermore, I will also be discussing several cross section measurements that are important for the interpretation of the data collected from these activation products.


    Sri Handayani


    Full Text Available The aim of this research is to determine the optimum time of reaction and concentration of hydroxide ion on chalcone, 4-methoxychalcone and 3,4-dimethoxychalcone synthesis. Chalcone and its derivatives were synthesized by dissolving KOH in ethanol followed by dropwise addition of acetophenone and benzaldehyde. Then, the mixture was stirred for several hours. Three benzaldehydes has been used, i.e : benzaldehyde, p-anysaldehyde and veratraldehyde. The time of reaction was varied for, 12, 18, 24, 30 and 36 hours. Furthermore, on the optimum reaction time for each benzaldehyde the hydroxyl ion concentration was varied from 5,7,9,11 and 13%(w/v. The results of this research suggested that the optimum time of chalchone synthesis was 12 hours, while, 4-methoxychalcone and 3,4-dimethoxychalcone were 30 hours. The optimum concentration of hydroxide ion of chalcone synthesis was 13% and for 4-methoxychalcone and 3,4-dimethoxychalcone were 11%. Keywords: Chalcone synthesis, time of reaction, hydroxide ion concentration.

  7. Surface concentration nonuniformities resulting from chronoamperometry of a reversible reaction at an ultramicrodisk electrode

    Britz, Dieter H.; Strutwolf, Jörg


    The chronoamperometric experiment at a disk electrode was simulated, assuming a reversible reaction. When the diffusion coefficients of the two substances involved are different, there appears a surface concentration non- uniformity in the radial direction, exhibiting a maximum effect in time. At...

  8. Effects of dissolved organic matter (DOM) at environmentally relevant carbon concentrations on atrazine degradation by Chelatobacter heintzii SalB.

    Cheyns, Karlien; Calcoen, Jasper; Martin-Laurent, Fabrice; Bru, David; Smolders, Erik; Springael, Dirk


    The dissolved organic matter (DOM) is the term used for organic components of natural origin present in the soil solution and is probably the most available C-source that primes microbial activity in subsoils. Contrasting effects of organic C components on pesticide degradation have been reported; however, most studies have used model organic compounds with compositions and concentrations which differ substantially from those found in the environment. Degradation of atrazine (AT) by Chelatobacter heintzii SalB was monitored in liquid batch assays in the absence or presence of well-defined model C compounds (glucose, gluconate and citrate) as model DOM (mDOM) or complex, less-defined, environmental DOM solutions (eDOM: isolated humic substances, soil and plant residue extracts) at environmentally relevant concentrations. Glucose significantly increased AT degradation rate by more than a factor of 8 at and above 2.5 mg C L( - 1). Optical density measurements showed that this stimulation is related to microbial growth. Gluconate and citrate had no effects unless at non-relevant concentrations (1,000 mg DOC L( - 1)) at which stimulations (gluconate) or inhibitions (citrate) were found. The effects of eDOM added at 10 mg DOC L( - 1) on AT degradation were generally small. The AT degradation time was reduced by factors 1.4-1.9 in the presence of humic acids and eDOM from soils amended with plant residues; however, no effects were found for fulvic acids or eDOM from a soil leachate solution or extracted from unamended peat or forest soil. In conclusion, DOM supplied as both mDOM and eDOM did not inhibit AT degradation at environmentally relevant concentrations, and stimulation can be found for selected DOM samples and this is partly related to its effect on growth.

  9. Nanoscale zerovalent iron (nZVI) at environmentally relevant concentrations induced multigenerational reproductive toxicity in Caenorhabditis elegans.

    Yang, Ying-Fei; Chen, Pei-Jen; Liao, Vivian Hsiu-Chuan


    Nanoscale zerovalent iron (nZVI) is widely used with large scale for environmental remediation for in situ or ex situ applications. The potential impact of nZVI on biota at environmentally relevant concentrations needs to be elucidated. In this study, the reproductive toxicities of three irons species: carboxymethyl cellulose (CMC)-stabilized nZVI, nanoscale iron oxide (nFe3O4), and ferrous ion (Fe(II)aq) in the soil-dwelling nematode Caenorhabditis elegans were examined. In addition, the generational transfer of reproductive toxicity of CMC-nZVI on C. elegans was investigated. The results showed that CMC-nZVI, nFe3O4, and Fe(II)aq did not cause significant mortality after 24 h exposure at the examined concentrations. Reproductive toxicity assays revealed that CMC-nZVI, nFe3O4, and Fe(II)aq significantly decreased offsprings in parental generation (F0) in accompany with the increased intracellular reactive oxygen species (ROS). Furthermore, the reproductive toxicity of CMC-nZVI at environmentally relevant concentrations was transferrable from the F0 to the F1 and F2 generations, but then recovered in the F3 and F4 generations. Further evidence showed that total irons were accumulated in the F0 and F1 generations of C. elegans after CMC-nZVI parental exposure. This study demonstrated that environmentally relevant concentrations of CMC-nZVI induced multigenerational reproductive toxicity which can be ascribed to its high production of ROS in F0 generation, toxicity of Fe(II)aq, and iron accumulation in C. elegans. Since nZVI is widely used for environmental remediation, considering the multigenerational toxicity, this study thus implicates a potential environmental risk of nZVI-induced nanotoxicity in the environment.

  10. Molecular control of TiO₂-NPs toxicity formation at predicted environmental relevant concentrations by Mn-SODs proteins.

    Yinxia Li

    Full Text Available With growing concerns of the safety of nanotechnology, the in vivo toxicity of nanoparticles (NPs at environmental relevant concentrations has drawn increasing attentions. We investigated the possible molecular mechanisms of titanium nanoparticles (Ti-NPs in the induction of toxicity at predicted environmental relevant concentrations. In nematodes, small sizes (4 nm and 10 nm of TiO₂-NPs induced more severe toxicities than large sizes (60 nm and 90 nm of TiO₂-NPs on animals using lethality, growth, reproduction, locomotion behavior, intestinal autofluorescence, and reactive oxygen species (ROS production as endpoints. Locomotion behaviors could be significantly decreased by exposure to 4-nm and 10-nm TiO₂-NPs at concentration of 1 ng/L in nematodes. Among genes required for the control of oxidative stress, only the expression patterns of sod-2 and sod-3 genes encoding Mn-SODs in animals exposed to small sizes TiO₂-NPs were significantly different from those in animals exposed to large sizes of TiO₂-NPs. sod-2 and sod-3 gene expressions were closely correlated with lethality, growth, reproduction, locomotion behavior, intestinal autofluorescence, and ROS production in TiO₂-NPs-exposed animals. Ectopically expression of human and nematode Mn-SODs genes effectively prevented the induction of ROS production and the development of toxicity of TiO₂-NPs. Therefore, the altered expression patterns of Mn-SODs may explain the toxicity formation for different sizes of TiO₂-NPs at predicted environmental relevant concentrations. In addition, we demonstrated here a strategy to investigate the toxicological effects of exposure to NPs upon humans by generating transgenic strains in nematodes for specific human genes.

  11. Cork stoppers as an effective sorbent for water treatment: the removal of mercury at environmentally relevant concentrations and conditions.

    Lopes, Cláudia B; Oliveira, Joana R; Rocha, Luciana S; Tavares, Daniela S; Silva, Carlos M; Silva, Susana P; Hartog, Niels; Duarte, Armando C; Pereira, E


    The technical feasibility of using stopper-derived cork as an effective biosorbent towards bivalent mercury at environmentally relevant concentrations and conditions was evaluated in this study. Only 25 mg/L of cork powder was able to achieve 94 % of mercury removal for an initial mercury concentration of 500 μg/L. It was found that under the conditions tested, the efficiency of mercury removal expressed as equilibrium removal percentage does not depend on the amount of cork or its particle size, but is very sensitive to initial metal concentration, with higher removal efficiencies at higher initial concentrations. Ion exchange was identified as one of the mechanisms involved in the sorption of Hg onto cork in the absence of ionic competition. Under ionic competition, stopper-derived cork showed to be extremely effective and selective for mercury in binary mixtures, while in complex matrices like seawater, moderate inhibition of the sorption process was observed, attributed to a change in mercury speciation. The loadings achieved are similar to the majority of literature values found for other biosorbents and for other metals, suggesting that cork stoppers can be recycled as an effective biosorbent for water treatment. However, the most interesting result is that equilibrium data show a very rare behaviour, with the isotherm presenting an almost square convex shape to the concentration axis, with an infinite slope for an Hg concentration in solution around 25 μg/L.

  12. 24. The transcription factors and the relevant signaling pathways activated by low concentration MNNG


    Aims: To explore the transcription factors and related signal transduction pathways activated in the alkylating agents N-methyl-N'-nitro-N-nitrosoguanindine (MNNG) exposed cells which may involved in the mechanism of MNNG induced changes of gene expression, especially the elevation of DNA polymerase β expression and also the consequence of JNK kinase activation which were reported previously in this lab. Methods: Clontech Mercury pathway profiling system containing 8 different vectors in which a specific response element is located upstream from the SEAP-reporter gene were employed to detect the transcription factor activation in Vero cells treated with 0.2 μmol/L MNNG for 2 hours. Thoroughly, CREB phosphorylation, protein kinase A (PKA) and the cellular cAMP content were also assayed with PhosphoPlus CREB (ser-133) antibody kit, protein kinase assay kit and cAMP RIA kit respectively. Results: Among 8 different response elements, the expression of the reporter gene governed by the transcription factors CREB (cAMP response element binding protein), AP1 (activator protein 1), NF-κB (nuclear factor κ B) were elevated by 1.3, 1.4 and 1.3 times higber than control respectively. The level of activated CREB by Ser-133 phosphorylation was 2.08 times higher than control in cells treated with MNNG for 60 min, as measured by immunoblotting. The activity of CREB upstream kinase protein kinase A (PKA), which can phosphorylate CREB on ser-133 was also activated, and the activation peaked at 60 min (11.03±2.80 arbitrary units vs 0.86±0.43 of control). Also, cAMP levels were significantly raised after 60-minute-treatment, 1.52 times higher vs those in solvent control. Conclusion: In addition of previously reported JNK activation, we show here that low concentration alkylating agent MNNG can also activate the cAMP-PKA and NF-κB pathway. These in consequence induce the activation of transcription factors APl, CREB and NF-κB, which may related to the MNNG induced changes in

  13. Clinically relevant HOCl concentrations reduce clot retraction rate via the inhibition of energy production in platelet mitochondria.

    Misztal, T; Rusak, T; Tomasiak, M


    Using porcine blood, we examined the impact of hypochlorite, product of activated inflammatory cells, on clot retraction (CR), an important step of hemostasis. We found that, in vitro, HOCl is able to reduce CR rate and enlarge final clot size in whole blood (t.c. 100 μM), platelet-rich plasma (PRP) threshold concentration (t.c. 50 μM), and an artificial system (washed platelets and fibrinogen) (t.c. 25 nM). Combination of low HOCl and peroxynitrite concentrations resulted in synergistic inhibition of CR by these stressors. Concentrations of HOCl completely inhibiting CR failed to affect the kinetics of coagulation measured in PRP and in platelet-free plasma. Concentrations of HOCl reducing CR rate in PRP augmented production of lactate, inhibited consumption of oxygen by platelets, and decreased total adenosine triphosphate (ATP) content in PRP-derived clots. In an artificial system, concentrations of HOCl resulting in inhibition of CR (25-100 nM) reduced mitochondrial transmembrane potential and did not affect actin polymerization in thrombin-stimulated platelets. These concentrations of HOCl failed to affect the adhesion of washed platelets to fibrinogen and to evoke sustained calcium signal, thus excluding stressor action on glycoprotein IIb/IIIa receptors. Exogenously added Mg-ATP almost completely recovered HOCl-mediated retardation of CR. Concentrations of HOCl higher than those affecting CR reduced thromboelastometric variables (maximum clot firmness and α angle). We conclude that low clinically relevant HOCl concentrations may evoke the inhibition of CR via the reduction of platelet contractility resulted from malfunction of platelet mitochondria. At the inflammatory conditions, CR may be the predominant HOCl target.

  14. Hydrogen concentrations as an indicator of the predominant terminal electron-accepting reactions in aquatic sediments

    Lovley, D.R.; Goodwin, S.


    Factors controlling the concentration of dissolved hydrogen gas in anaerobic sedimentary environments were investigated. Results, presented here or previously, demonstrated that, in sediments, only microorganisms catalyze the oxidation of H2 coupled to the reduction of nitrate, Mn(IV), Fe(III), sulfate, or carbon dioxide. Theoretical considerations suggested that, at steady-state conditions, H2 concentrations are primarily dependent upon the physiological characteristics of the microorganism(s) consuming the H2 and that organisms catalyzing H2 oxidation, with the reduction of a more electrochemically positive electron acceptor, can maintain lower H2 concentrations than organisms using electron acceptors which yield less energy from H2 oxidation. The H2 concentrations associated with the specified predominant terminal electron-accepting reactions in bottom sediments of a variety of surface water environments were: methanogenesis, 7-10 nM; sulfate reduction, 1-1.5 nM; Fe(III) reduction, 0.2 nM; Mn(IV) or nitrate reduction, less than 0.05 nM. Sediments with the same terminal electron acceptor for organic matter oxidation had comparable H2 concentrations, despite variations in the rate of organic matter decomposition, pH, and salinity. Thus, each terminal electron-accepting reaction had a unique range of steady-state H2 concentrations associated with it. Preliminary studies in a coastal plain aquifer indicated that H2 concentrations also vary in response to changes in the predominant terminal electron-accepting process in deep subsurface environments. These studies suggest that H2 measurements may aid in determining which terminal electron-accepting reactions are taking place in surface and subsurface sedimentary environments. ?? 1988.

  15. Viability of primary osteoblasts after treatment with tenofovir alafenamide: Lack of cytotoxicity at clinically relevant drug concentrations

    Callebaut, Christian; Liu, Yang; Babusis, Darius; Ray, Adrian; Miller, Michael; Kitrinos, Kathryn


    Tenofovir alafenamide (TAF) is a phosphonoamidate prodrug of the nucleotide HIV reverse transcriptase inhibitor tenofovir (TFV). TAF is approved for the treatment of HIV-1 infection as part of the single-tablet regimen containing elvitegravir, cobicistat, emtricitabine, and TAF. When dosed once-daily, TAF results in approximately 90% lower levels of plasma TFV and a 4-fold increase in intracellular TFV-diphosphate (TFV-DP) in PBMCs compared with the TFV prodrug tenofovir disoproxil fumarate (TDF). Several antiretrovirals, including TDF, have been associated with bone mineral density decreases in patients; the effect of clinically relevant TAF concentrations on primary osteoblast viability was therefore assessed in vitro. Studies in PBMCs determined that a 2-hour TAF exposure at concentrations similar to human plasma Cmax achieved intracellular TFV-DP levels comparable to those observed after the maximum recommended human dose of 25 mg TAF. Comparable intracellular TFV-DP levels were achieved in primary osteoblasts with 2-hour TAF exposure daily for 3 days at concentrations similar to those used for PBMCs (100–400 nM). No change in cell viability was observed in either primary osteoblasts or PBMCs. The mean TAF CC50 in primary osteoblasts after 3 days of daily 2-hour pulses was >500 μM, which is >1033 times higher than the TAF maximum recommended human dose plasma Cmax. In summary, primary osteoblasts were not preferentially loaded by TAF compared with PBMCs, with comparable TFV-DP levels achieved in both cell types. Furthermore, there was no impact on osteoblast cell viability at clinically relevant TAF concentrations. PMID:28182625

  16. Effect of Heteroatom Concentration in SSZ-13 on the Methanol-to-Olefins Reaction

    Deimund, Mark A.; Harrison, Luke; Lunn, Jonathan D.; Liu, Yu; Malek, Andrzej; Shayib, Ramzy; Davis, Mark E.


    SSZ-13 materials have been synthesized with varying amounts of Al to produce samples with different concentrations of Brønsted acid sites, and consequently, these SSZ-13 materials contain increasing numbers of paired Al heteroatoms with increasing Al content. These materials were then characterized and tested as catalysts for the methanol-to-olefins (MTO) reaction at 400 °C and 100% methanol conversion under atmospheric pressure. A SAPO-34 sample was also synthesized and tested for comparison...

  17. Handheld Device Adapted to Smartphone Cameras for the Measurement of Sodium Ion Concentrations at Saliva-Relevant Levels via Fluorescence

    Michelle Lipowicz


    Full Text Available The use of saliva sampling as a minimally-invasive means for drug testing and monitoring physiology is a subject of great interest to researchers and clinicians. This study describes a new optical method based on non-axially symmetric focusing of light using an oblate spheroid sample chamber. The device is simple, lightweight, low cost and is easily attached to several different brands/models of smartphones (Apple, Samsung, HTC and Nokia for the measurement of sodium ion levels at physiologically-relevant saliva concentrations. The sample and fluorescent reagent solutions are placed in a specially-designed, lightweight device that excludes ambient light and concentrates 470-nm excitation light, from a low-power photodiode, within the sample through non-axially-symmetric refraction. The study found that smartphone cameras and post-image processing quantitated sodium ion concentration in water over the range of 0.5–10 mM, yielding best-fit regressions of the data that agree well with a data regression of microplate luminometer results. The data suggest that fluorescence can be used for the measurement of salivary sodium ion concentrations in low-resource or point-of-care settings. With further fluorescent assay testing, the device may find application in a variety of enzymatic or chemical assays.

  18. New Improved Indirect Measurement of the 19F(p, α)16O Reaction at Energies of Astrophysical Relevance

    Indelicato, I.; La Cognata, M.; Spitaleri, C.; Burjan, V.; Cherubini, S.; Gulino, M.; Hayakawa, S.; Hons, Z.; Kroha, V.; Lamia, L.; Mazzocco, M.; Mrazek, J.; Pizzone, R. G.; Romano, S.; Strano, E.; Torresi, D.; Tumino, A.


    Fluorine abundance determination is of great importance in stellar physics to understand s-elements production and mixing processes in asymptotic giant branch (AGB) stars. Up to now, theoretical models overproduce F abundances in AGB stars with respect to the observed values, thus calling for further investigation of the reactions involving fluorine. In particular, the 19F(p, α)16O reaction is the main destruction channel of fluorine at the bottom of the convective envelope in AGB stars, an H-rich environment where it can experience temperatures high enough to determine its destruction, owing to additional mixing processes. In this paper the Trojan horse method (THM) was used to extract the 19F(p, α 0)16O S-factor in the energy range of astrophysical interest (E cm ≈ 0-1 MeV). This is the most relevant channel at the low temperatures (few 107 K) characterizing the bottom of the convective envelope, according to current knowledge. A previous indirect experiment using the THM has observed three resonances in the energy regions below E cm ≈ 450 keV. These energies correspond to typical AGB temperatures, thus implying a significant increase in the reaction rate. Statistics are scarce for performing an accurate separation between resonances, preventing one from drawing a quantitative conclusion about their total widths and spin parities. Before THM measurement, only extrapolations were available below about 500 keV, showing a non-resonant behavior that sharply contradicts the trend of the astrophysical factor at higher energies. A new experiment has been performed to verify the measured TH astrophysical factor and to perform more accurate spectroscopy of the involved resonances.

  19. Effects of the boscalid fungicide Filan® on the marine amphipod Allorchestes compressa at environmentally relevant concentrations.

    Vu, Hung T; Keough, Michael J; Long, Sara M; Pettigrove, Vincent J


    Fungicides are widely used in agriculture to control fungal diseases. After application, fungicides can be transported offsite to surface and groundwater and ultimately enter estuarine and marine environments. The presence of fungicides in the marine environment may pose risks to marine organisms, but little is known about fungicide effects on these organisms, especially invertebrates. The present study investigated the effects of the commonly used boscalid fungicide Filan® on life history traits, feeding rate, and energy reserves (lipid, glycogen, and protein content) of the marine amphipod Allorchestes compressa over 6 wk under laboratory conditions. Amphipods were exposed to 3 concentrations of Filan (1 μg, 10 μg, and 40 μg active ingredient [a.i.]/L), with 5 replicates per treatment. Lipid content and reproduction were the most sensitive measures of effect, with lipid content reduced by 53.8% at the highest concentration. Survival, growth, and other energy reserves of amphipods were also negatively affected by Filan, and the effects were concentration dependent. Antennal deformities were incidentally observed on the amphipods at a concentration of 40 μg a.i./L. The results of the present study indicate comprehensive effects of the boscalid fungicide Filan on A. compressa at environmentally relevant concentrations. The decline or absence of A. compressa in marine ecosystems could impair the ecosystem function because of their important role in trophic transfer and nutrient recycling. The authors' results suggest that even though the use of fungicides is often regarded as posing only a minor risk to aquatic organisms, the assessment of their long-term effects is critical.

  20. Competition reactions of H2O•+ radical in concentrated Cl- aqueous solutions: picosecond pulse radiolysis study.

    El Omar, Abdel Karim; Schmidhammer, Uli; Rousseau, Bernard; LaVerne, Jay; Mostafavi, Mehran


    Picosecond pulse-probe radiolysis measurements of highly concentrated Cl(-) aqueous solutions are used to probe the oxidation mechanism of the Cl(-). The transient absorption spectra are measured from 340 to 710 nm in the picosecond range for the ultrafast electron pulse radiolysis of halide solutions at different concentrations up to 8 M. The amount of Cl(2)(•-) formation within the electron pulse increases notably with increasing Cl(-) concentration. Kinetic measurements reveal that the direct ionization of Cl(-) cannot solely explain the significant amount of fast Cl(2)(•-) formation within the electron pulse. The results suggest that Cl(-) reacts with the precursor of the OH(•) radical, i.e., H(2)O(•+) radical, to form Cl(•) atom within the electron pulse and the Cl(•) atom reacts subsequently with Cl(-) to form Cl(2)(•-) on very short time scales. The proton transfer reaction between H(2)O(•+) and the water molecule competes with the electron transfer reaction between Cl(-) and H(2)O(•+). Molecular dynamics simulations show that number of water molecules in close proximity decreases with increasing concentration of the salt (NaCl), confirming that for highly concentrated solutions the proton transfer reaction between H(2)O(•+) and a water molecule becomes less efficient. Diffusion-kinetic simulations of spur reactions including the direct ionization of Cl(-) and hole scavenging by Cl(-) show that up to 30% of the H(2)O(•+) produced by the irradiation could be scavenged for solutions containing 5.5 M Cl(-). This process decreases the yield of OH(•) radical in solution on the picosecond time scale. The experimental results for the same concentration of Cl(-) at a given absorbed dose show that the radiation energy absorbed by counterions is transferred to Cl(-) or water molecules and the effect of the countercation such as Li(+), K(+), Na(+), and Mg(2+) on the oxidation yield of Cl(-) is negligible.

  1. Spontaneous encapsulation and concentration of biological macromolecules in liposomes: an intriguing phenomenon and its relevance in origins of life.

    de Souza, Tereza Pereira; Fahr, Alfred; Luisi, Pier Luigi; Stano, Pasquale


    One of the main open questions in origin of life research focuses on the formation, by self-organization, of primitive cells composed by macromolecular compounds enclosed within a semi-permeable membrane. A successful experimental strategy for studying the emergence and the properties of primitive cells relies on a synthetic biology approach, consisting in the laboratory assembly of cell models of minimal complexity (semi-synthetic minimal cells). Despite the recent advancements in the construction and characterization of synthetic cells, an important physical aspect related to their formation is still not well known, namely, the mechanism of solute entrapment inside liposomes (in particular, the entrapment of macromolecules). In the past years, we have investigated this phenomenon and here we shortly review our experimental results. We show how the detailed cryo-transmission electron microscopy analyses of liposome populations created in the presence of ferritin (taken as model protein) or ribosomes have revealed that a small fraction of liposomes contains a high number of solutes, against statistical expectations. The local (intra-liposomal) macromolecule concentration in these liposomes largely exceeds the bulk concentration. A similar behaviour is observed when multi-molecular reaction mixtures are used, whereby the reactions occur effectively only inside those liposomes that have entrapped high number of molecules. If similar mechanisms operated in early times, these intriguing results support a scenario whereby the formation of lipid compartments plays an important role in concentrating the components of proto-metabolic systems-in addition to their well-known functions of confinement and protection.

  2. Computational studies of atmospherically-relevant chemical reactions in water clusters and on liquid water and ice surfaces.

    Gerber, R Benny; Varner, Mychel E; Hammerich, Audrey D; Riikonen, Sampsa; Murdachaew, Garold; Shemesh, Dorit; Finlayson-Pitts, Barbara J


    isolated defects where it involves formation of H3O(+)-acid anion contact ion pairs. This behavior is found in simulations of a model of the ice quasi-liquid layer corresponding to large defect concentrations in crystalline ice. The results are in accord with experiments. (iv) Ionization of acids on wet quartz. A monolayer of water on hydroxylated silica is ordered even at room temperature, but the surface lattice constant differs significantly from that of crystalline ice. The ionization processes of HCl and H2SO4 are of high yield and occur in a few picoseconds. The results are in accord with experimental spectroscopy. (v) Photochemical reactions on water and ice. These simulations require excited state quantum chemical methods. The electronic absorption spectrum of methyl hydroperoxide adsorbed on a large ice cluster is strongly blue-shifted relative to the isolated molecule. The measured and calculated adsorption band low-frequency tails are in agreement. A simple model of photodynamics assumes prompt electronic relaxation of the excited peroxide due to the ice surface. SEMD simulations support this, with the important finding that the photochemistry takes place mainly on the ground state. In conclusion, dynamics simulations using quantum chemical potentials are a useful tool in atmospheric chemistry of water media, capable of comparison with experiment.

  3. Behavior toxicity to Caenorhabditis elegans transferred to the progeny after exposure to sulfamethoxazole at environmentally relevant concentrations

    Zhenyang Yu; Lei Jiang; Daqiang Yin


    Sulfamethoxazole (SMX) is one of the most common detected antibiotics in the environment. In order to study whether SMX can affect behavior and growth and whether these effects could be transferred to the progeny, Caenorhabditis elegans was exposed at environmentally relevant concentrations for 24, 48, 72 and 96 hr, respectively. After exposure, the exposed parent generation (Po) was measured for behavior and growth indicators, which were presented as percentage of controls (POC). Then their corresponding unexposed progeny (F1) was separated and measured for the same indicators. The lowest POC for Po after 96 hr-exposure at 100 mg/L were 37.8%, 12.7%, 45.8% and 70.1% for body bending frequency (BBF), reversal movement (RM), Omega turns (OT) and body length (BL), respectively. And F1 suffered defects with the lowest POC as 55.8%, 24.1%, 48.5% and 60.7% for BBF, RM, OT and BL, respectively. Defects in both Po and F1 showed a time- and concentration-dependent fashion and behavior indicators showed better sensitivity than growth indicator. The observed effects on F1 demonstrated the transferable properties of SMX. Defects of SMX at environmental concentrations suggested that it is necessary to perform further systematical studies on its ecological risk in actual conditions.

  4. Investigation on Concentrated V(IV)/V(V) Redox Reaction by Rotating Disc Voltammetry

    WEN Yue-Hua; ZHANG Hua-Min; QIAN Peng; MA Hai-Peng; YI Bao-Lian; YANG Yu-Sheng


    The kinetic characteristics of the concentrated V(IV)/V(V) couple have been studied at a glassy carbon electrode in sulfuric acid using rotating-disc electrode and cyclic voltammetry. The kinetics of the V(IV)/V(V) redox couple reaction was found to be electrochemically quasi-reversible with the slower kinetics for the V(V) reduction than that for the V(IV) oxidation. And, dependence of diffusion coefficients and kinetic parameters of V(IV) species on the V(IV) and H25O4 concentration was investigated. It is shown that the concentration of active species V(IV)centration, the diffusion coefficients of V(IV) were gradually reduced whereas its kinetics was improved considerably,espicially in the case of Ⅴ(Ⅳ)and H2SO4 up to 2 and 4 mol·L-1.

  5. An electron microscopy based method for the detection and quantification of nanomaterial number concentration in environmentally relevant media

    Prasad, A. [School of Geography, Earth and Environmental Sciences, College of Life and Environmental Sciences, University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom); Lead, J.R., E-mail: [School of Geography, Earth and Environmental Sciences, College of Life and Environmental Sciences, University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom); Center for Environmental Nanoscience and Risk, Department of Environmental Health Sciences, Arnold School of Public Health, University South Carolina, Columbia 29208, SC (United States); Baalousha, M., E-mail: [Center for Environmental Nanoscience and Risk, Department of Environmental Health Sciences, Arnold School of Public Health, University South Carolina, Columbia 29208, SC (United States)


    Improved detection and characterization of nanomaterials (NMs) in complex environmental media requires the development of novel sampling approaches to improve the detection limit to be close to environmentally realistic concentrations. Transmission electron microscopy (TEM) is an indispensable metrological tool in nanotechnology and environmental nanoscience due to its high spatial resolution and analytical capabilities when coupled to spectroscopic techniques. However, these capabilities are hampered by the conventional sample preparation methods, which suffer from low NM recovery. The current work presents a validated, fully quantitative sampling technique for TEM that overcomes conventional sample preparation shortcomings, and thus enables the use of TEM for measurement of particle number concentration and their detection in complex media at environmentally realistic concentrations. This sampling method is based on ultracentrifugation of NMs from suspension onto a poly-L-lysine (PLL) functionalized TEM grid, using active deposition (by ultracentrifugation) and retention (by PLL interactions with NM surface) of NMs on the substrate, enabling fully quantitative analysis. Similar analysis with AFM was satisfactory in simple media but the lack of chemical-selectivity of AFM limits its applicability for the detection of NMs in complex environmental samples. The sampling approach was validated using both citrate- and PVP-coated AuNMs in pure water, which demonstrated an even distribution of NM on the TEM grid and high NM recovery (80–100%) at environmentally relevant NM concentrations (ca. 0.20–100 μg L{sup −1}). The applicability of the sampling method to complex environmental samples was demonstrated by the quantification of particle number concentration of AuNMs in EPA soft water (with and without Suwannee River fulvic acid) and lake water. This sample preparation approach is also applicable to other types of NMs with some modifications (e.g. centrifugation

  6. Effects of glyphosate at environmentally relevant concentrations on the growth of and microcystin production by Microcystis aeruginosa.

    Zhang, Quan; Zhou, Hang; Li, Zhe; Zhu, Jianqiang; Zhou, Cong; Zhao, Meirong


    The use of glyphosate, which is a well-known sterilant herbicide, has been growing rapidly because the area under the cultivation of genetically modified crops that are tolerant to this herbicide has increased. Glyphosate can enter into aquatic systems through many different ways. However, information on the potential risks of glyphosate at environmentally relevant levels to aquatic systems is still limited. In this study, we selected the cyanobacterium Microcystis aeruginosa FACHB-905 (M. aeruginosa) as a model organism to evaluate the effects of glyphosate at environmentally relevant concentrations on the former's growth and microcystin (MC) production. Our results show that low levels of glyphosate stimulate the growth of M. aeruginosa. Subsequently, there was significant increase in the total MC-LR and intracellular MC-LR, but not in extracellular MC-LR, after exposure to 0.1-2 mg/L of glyphosate. The increase in total MC-LR is mainly due to the effects of glyphosate on the cell density of M. aeruginosa. The data provided here show that low level of glyphosate in a water body is a potential environmental risk factor that stimulates the growth and enhances MC production in M. aeruginosa, which should arouse great concern.

  7. Commonly prescribed β-lactam antibiotics induce C. trachomatis persistence/stress in culture at physiologically relevant concentrations.

    Jennifer eKintner


    Full Text Available Chlamydia trachomatis, the most common bacterial sexually transmitted disease agent worldwide, enters a viable, non-dividing and non-infectious state (historically termed persistence and more recently referred to as the chlamydial stress response when exposed to penicillin G in culture. Notably, penicillin G-exposed chlamydiae can reenter the normal developmental cycle upon drug removal and are resistant to azithromycin-mediated killing. Because penicillin G is less frequently prescribed than other β-lactams, the clinical relevance of penicillin G-induced chlamydial persistence/stress has been questioned. The goal of this study was to determine whether more commonly used penicillins also induce C. trachomatis serovar E persistence/stress. All penicillins tested, as well as clavulanic acid, induced formation of aberrant, enlarged reticulate bodies (called aberrant bodies or AB characteristic of persistent/stressed chlamydiae. Exposure to the penicillins and clavulanic acid also reduced chlamydial infectivity by >95%. None of the drugs tested significantly reduced chlamydial unprocessed 16S rRNA or genomic DNA accumulation, indicating that the organisms were viable, though non-infectious. Finally, recovery assays demonstrated that chlamydiae rendered essentially non-infectious by exposure to ampicillin, amoxicillin, carbenicillin, piperacillin, penicillin V and clavulanic acid recovered infectivity after antibiotic removal. These data definitively demonstrate that several commonly used penicillins induce C. trachomatis persistence/stress at clinically relevant concentrations.

  8. What is the relevance of contact allergy to sodium metabisulfite and which concentration of the allergen should we use?

    Ralph, Nicola; Verma, Saroj; Merry, Subha; Lally, Aoife; Kirby, Brian; Collins, Paul


    The prevalence of contact allergy to sodium metabisulfite (SMB) has increased from the range of 1.4% to 1.7% to the range of 3.4% to 6.8% in published series over the past 20 years. The aims of this study were to review contact allergy to SMB in our cohort and to investigate different concentrations to define the most appropriate concentration for patch testing. Patient records were reviewed between February 2009 and December 2011 to obtain information on patient demographics, clinical presentation, and prevalence of contact allergy to SMB. Patients attending for patch testing, between January 2012 and June 2013, were tested with 3 strengths of SMB as part of the British standard series (1%, 0.1%, and 0.01%). Nine hundred ninety-six patients were patch tested to the British standard series including SMB 1% in petrolatum between February 2009 and June 2013, and 70 (7%) were positive. In the prospective group, 380 were tested to 3 concentrations of SMB (1.0%, 0.1%, and 0.01%). Fourteen patients (3.68%) had a positive patch test with 1% SMB, 7 to 0.1% SMB, and 3 to 0.01% SMB. There was exposure to SMB in 10 patients who cleared with avoidance at review 3 months later. The most frequent location of rash included face, hands, vulval, and perianal region. Our study confirms reports of increasing prevalence of SMB allergy. A detailed review of exposure in the prospective study showed that SMB is relevant in most patients, and 1% in petrolatum is the best concentration for patch testing.

  9. Glucocorticoid activity detected by in vivo zebrafish assay and in vitro glucocorticoid receptor bioassay at environmental relevant concentrations.

    Chen, Qiyu; Jia, Ai; Snyder, Shane A; Gong, Zhiyuan; Lam, Siew Hong


    Glucocorticoids are pharmaceutical contaminants of emerging concern due to their incomplete removal during wastewater treatment, increased presence in aquatic environment and their biological potency. The zebrafish is a popular model for aquatic toxicology and environmental risk assessment. This study aimed to determine if glucocorticoids at environmental concentrations would perturb expression of selected glucocorticoid-responsive genes in zebrafish and to investigate their potentials as an in vivo zebrafish assay in complementing in vitro glucocorticoid receptor bioassay. The relative expression of eleven glucocorticoid-responsive genes in zebrafish larvae and liver of adult male zebrafish exposed to three representative glucocorticoids (dexamethasone, prednisolone and triamcinolone) was determined. The expression of pepck, baiap2 and pxr was up-regulated in zebrafish larvae and the expression of baiap2, pxr and mmp-2 was up-regulated in adult zebrafish exposed to glucocorticoids at concentrations equivalent to total glucocorticoids reported in environmental samples. The responsiveness of the specific genes were sufficiently robust in zebrafish larvae exposed to a complex environmental sample detected with in vitro glucocorticoid activity equivalent to 478 pM dexamethasone (DEX-EQ) and confirmed to contain low concentration (0.2 ng/L or less) of the targeted glucocorticoids, and possibly other glucocorticoid-active compounds. The findings provided in vivo relevance to the in vitro glucocorticoid activity and suggested that the environmental sample can perturb glucocorticoid-responsive genes in its original, or half the diluted, concentration as may be found in the environment. The study demonstrated the important complementary roles of in vivo zebrafish and in vitro bioassays coupled with analytical chemistry in monitoring environmental glucocorticoid contaminants.

  10. Enrofloxacin at environmentally relevant concentrations enhances uptake and toxicity of cadmium in the earthworm Eisenia fetida in farm soils

    Li, Yinsheng, E-mail: [School of Agriculture and Biology, Shanghai Jiao Tong University, Shanghai 200240 (China); Tang, Hao; Hu, Yingxiu; Wang, Xiuhong; Ai, Xiaojie; Tang, Li [School of Agriculture and Biology, Shanghai Jiao Tong University, Shanghai 200240 (China); Matthew, Cory [Institute of Agriculture & Environment, Massey University, Private Bag 11-222, Palmerston North 4442 (New Zealand); Cavanagh, Jo [Landcare Research, PO Box 40, Lincoln 7640 (New Zealand); Qiu, Jiangping [School of Agriculture and Biology, Shanghai Jiao Tong University, Shanghai 200240 (China)


    Highlights: • Enrofloxacin (EF) and cadmium (Cd) were independently adsorbed in soils. • EF accelerated and increased Cd bioaccumulation in earthworms. • At high concentration EF (10 mg kg{sup −1}) was toxic to earthworms. • EF enhanced Cd induced oxidative stress, and increased burrowing and respiration. • EF did not affect the Cd induced increase in metallothionein in earthworms. - Abstract: Individual and combined effects of enrofloxacin (EF) and cadmium (Cd) on the earthworm Eisenia fetida at environmentally relevant concentrations were investigated. EF is a veterinary antibiotic; Cd is an impurity in phosphatic fertiliser. For both, residues may accumulate in farm soils. In laboratory tests, over 98% of spiked EF was adsorbed by farm soils, with a half-life >8 weeks. However, earthworms absorbed less than 20% of spiked EF. Earthworms in soil with EF concentration 10 mg kg{sup −1} soil experienced transient oxidative stress and exhibited reduced burrowing activity and respiration after an 8-week exposure; EF at 0.1 and 1.0 mg kg{sup −1} soil did not elicit toxicity symptoms. When both were added, Cd did not affect EF uptake, but each increment of spiked EF increased Cd bioaccumulation and associated oxidative stress of earthworms, and also caused decreased burrow length and CO{sub 2} production. However, metallothionein induction was not affected. The enhanced toxicity of Cd to earthworms in the presence of EF at low environmental concentrations may have implications for the health and reproductive success of earthworm populations and highlights the importance of understanding effects of antibiotic contamination of farm soils, and of awareness of environmental effects from interaction between multiple contaminants.

  11. Comparison of the Oxidation Behaviors of High FeO Chromite and Magnetite Concentrates Relevant to the Induration of Ferrous Pellets

    Zhu, Deqing; Yang, Congcong; Pan, Jian; Li, Xiaobo


    Oxidation process plays an important role in producing sufficiently strong ferrous pellets for blast furnace, and the oxidation behavior of pellet feed greatly affects the quality of pellets. As a supplementary research to earlier published work, the present study fixes its particular attention on the fundamental oxidation behavior of a high FeO South African chromite concentrate in comparison to that of typical magnetite concentrate using differential scanning calorimetry, X-ray diffraction analysis, and thermogravimetry at various temperatures ranging from 473 K to 1273 K (200 °C to 1000 °C). The reaction mechanism and phase transformation during the oxidation process of chromite spinel is further explained by thermodynamics calculation performed by FactSage software. Besides, routine laboratory preheating-roasting test of single ore pellets is also conducted to reveal the relevance of oxidizability to the consolidation of pellets. The results show that the chromite spinel possesses much poorer oxidizability than magnetite, usually accompanying complex phase transformations via a preferential nucleation of Fe-rich sesquioxide from the chromite spinel matrix at low temperatures and thereafter the formation of Cr-rich sesquioxide on the substrate of Fe-rich phase at high temperatures. The oxidation of chromite spinel is inferior to that of magnetite from the viewpoint of thermodynamics and dynamic kinetics. Good inherent oxidizability of raw materials is found to have a positive effect on the induration process of pellet.

  12. Even low alcohol concentrations affect obstacle avoidance reactions in healthy senior individuals

    Nienhuis Bart


    Full Text Available Abstract Background Alcohol is a commonly used social drug and driving under influence is a well-established risk factor for traffic accidents1. To improve road safety, legal limits are set for blood alcohol concentration (BAC and driving, usually at 0.05% (most European countries or 0.08% (most US states, Canada and UK. In contrast, for walking there are no legal limits, yet there are numerous accounts of people stumbling and falling after drinking. Alcohol, even at these low concentrations, affects brain function and increases fall risk. An increased fall risk has been associated with impaired obstacle avoidance skills. Low level BACs are likely to affect obstacle avoidance reactions during gait, since the brain areas that are presumably involved in these reactions have been shown to be influenced by alcohol. Therefore we investigated the effect of low to moderate alcohol consumption on such reactions. Thirteen healthy senior individuals (mean(SD age: 61.5(4.4 years, 9 male were subjected to an obstacle avoidance task on a treadmill after low alcohol consumption. Fast stepping adjustments were required to successfully avoid suddenly appearing obstacles. Response times and amplitudes of the m. biceps femoris, a prime mover, as well as avoidance failure rates were assessed. Findings After the first alcoholic drink, 12 of the 13 participants already had slower responses. Without exception, all participants' biceps femoris response times were delayed after the final alcoholic drink (avg ± sd:180 ± 20 ms; p r = 0.6; p Conclusions The present results clearly show that even with BACs considered to be safe for driving, obstacle avoidance reactions are inadequate, late, and too small. This is likely to contribute to an increased fall risk. Therefore we suggest that many of the alcohol-related falls are the result of the disruptive effects of alcohol on the online corrections of the ongoing gait pattern when walking under challenging conditions.

  13. An electron microscopy based method for the detection and quantification of nanomaterial number concentration in environmentally relevant media.

    Prasad, A; Lead, J R; Baalousha, M


    Improved detection and characterization of nanomaterials (NMs) in complex environmental media requires the development of novel sampling approaches to improve the detection limit to be close to environmentally realistic concentrations. Transmission electron microscopy (TEM) is an indispensable metrological tool in nanotechnology and environmental nanoscience due to its high spatial resolution and analytical capabilities when coupled to spectroscopic techniques. However, these capabilities are hampered by the conventional sample preparation methods, which suffer from low NM recovery. The current work presents a validated, fully quantitative sampling technique for TEM that overcomes conventional sample preparation shortcomings, and thus enables the use of TEM for measurement of particle number concentration and their detection in complex media at environmentally realistic concentrations. This sampling method is based on ultracentrifugation of NMs from suspension onto a poly-l-lysine (PLL) functionalized TEM grid, using active deposition (by ultracentrifugation) and retention (by PLL interactions with NM surface) of NMs on the substrate, enabling fully quantitative analysis. Similar analysis with AFM was satisfactory in simple media but the lack of chemical-selectivity of AFM limits its applicability for the detection of NMs in complex environmental samples. The sampling approach was validated using both citrate- and PVP-coated AuNMs in pure water, which demonstrated an even distribution of NM on the TEM grid and high NM recovery (80-100%) at environmentally relevant NM concentrations (ca. 0.20-100 μg L(-1)). The applicability of the sampling method to complex environmental samples was demonstrated by the quantification of particle number concentration of AuNMs in EPA soft water (with and without Suwannee River fulvic acid) and lake water. This sample preparation approach is also applicable to other types of NMs with some modifications (e.g. centrifugation force and

  14. Regulation of NF-{kappa}B activity in astrocytes: effects of flavonoids at dietary-relevant concentrations

    Spilsbury, Alison [Reading School of Pharmacy, University of Reading, Reading RG6 6UB (United Kingdom); Vauzour, David; Spencer, Jeremy P.E. [Molecular Nutrition Group, Centre for Integrative Neuroscience and Neurodynamics, School of Chemistry, Food and Pharmacy, University of Reading, Reading RG6 6AP (United Kingdom); Rattray, Marcus, E-mail: [Reading School of Pharmacy, University of Reading, Reading RG6 6UB (United Kingdom)


    Highlights: Black-Right-Pointing-Pointer We tested the hypothesis that low concentrations of flavonoids inhibit NF-{kappa}B in astrocytes. Black-Right-Pointing-Pointer Primary cultured astrocytes possess a functional {kappa}B-system, measured using luciferase assays. Black-Right-Pointing-Pointer Seven flavonoids (100 nM-1 {mu}M) failed to reduce NF-{kappa}B activity in astrocytes. Black-Right-Pointing-Pointer Four flavonoids (100 nM-1 {mu}M) failed to reduce TNFa-stimulated NF-{kappa}B activity in astrocytes. Black-Right-Pointing-Pointer (-)-Epicatechin did not regulate nuclear translocation of the NF-{kappa}B subunit, p65. -- Abstract: Neuroinflammation plays an important role in the progression of neurodegenerative disorders such as Alzheimer's disease and Parkinson's disease. Sustained activation of nuclear transcription factor {kappa}B (NF-{kappa}B) is thought to play an important role in the pathogenesis of neurodegenerative disorders. Flavonoids have been shown to possess antioxidant and anti-inflammatory properties and we investigated whether flavonoids, at submicromolar concentrations relevant to their bioavailability from the diet, were able to modulate NF-{kappa}B signalling in astrocytes. Using luciferase reporter assays, we found that tumour necrosis factor (TNF{alpha}, 150 ng/ml) increased NF-{kappa}B-mediated transcription in primary cultures of mouse cortical astrocytes, which was abolished on co-transfection of a dominant-negative I{kappa}B{alpha} construct. In addition, TNF{alpha} increased nuclear localisation of p65 as shown by immunocytochemistry. To investigate potential flavonoid modulation of NF-{kappa}B activity, astrocytes were treated with flavonoids from different classes; flavan-3-ols ((-)-epicatechin and (+)-catechin), flavones (luteolin and chrysin), a flavonol (kaempferol) or the flavanones (naringenin and hesperetin) at dietary-relevant concentrations (0.1-1 {mu}M) for 18 h. None of the flavonoids modulated constitutive or

  15. Propofol at Clinically Relevant Concentrations Increases Neuronal Differentiation but Is Not Toxic to Hippocampal Neural Precursor Cells In Vitro

    Sall, Jeffrey W.; Stratmann, Greg; Leong, Jason; Woodward, Elliott; Bickler, Philip E.


    Background Propofol in the early postnatal period has been shown to cause brain cell death. One proposed mechanism for cognitive dysfunction after anesthesia is alteration of neural stem cell function and neurogenesis. We examined the effect of propofol on neural precursor or stem cells (NPCs) grown in vitro. Methods Hippocampal derived NPCs from postnatal day 2 rats were exposed to propofol or to Diprivan. NPCs were then analyzed for bromodeoxyuridine incorporation to measure proliferation. Cell death was measured by lactate dehydrogenase release. Immunocytochemistry was used to evaluate the expression of neuronal and glial markers in differentiating NPCs exposed to propofol. Results Propofol dose dependently increases the release of lactate dehydrogenase from NPCs under both proliferating and differentiating conditions at supraclinical concentrations (> 7.1μM). Both Diprivan and propofol had the same effect on NPCs. Propofol mediated release of lactate dehydrogenase is not inhibited by blocking the γ-aminobutyric acid type A receptor or extracellular calcium influx and is not mediated by caspase-3/7. Direct γ-aminobutyric acid type A receptor activation did not have the same effect. In differentiating NPCs 6 h of propofol at 2.1 μM increased the number neurons but not glial cells 4 days later. Increased neuronal differentiation was not blocked by Bicuculline. Conclusions Only supraclinical concentrations of propofol or Diprivan kill NPCs in culture by a non-γ-aminobutyric acid type A, noncaspase 3 mechanism. Clinically relevant doses of propofol increase neuronal fate choice by a non-γ-aminobutyric acid type A mechanism. PMID:23001052

  16. Minimal inhibitory concentrations of undissociated lactic, acetic, citric and propionic acid for Listeria monocytogenes under conditions relevant to cheese.

    Wemmenhove, Ellen; van Valenberg, Hein J F; Zwietering, Marcel H; van Hooijdonk, Toon C M; Wells-Bennik, Marjon H J


    Minimal inhibitory concentrations (MICs) of undissociated lactic acid were determined for six different Listeria monocytogenes strains at 30 °C and in a pH range of 4.2-5.8. Small increments in pH and acid concentrations were used to accurately establish the growth/no growth limits of L. monocytogenes for these acids. The MICs of undissociated lactic acid in the pH range of 5.2-5.8 were generally higher than at pH 4.6 for the different L. monocytogenes strains. The average MIC of undissociated lactic acid was 5.0 (SD 1.5) mM in the pH range 5.2-5.6, which is relevant to Gouda cheese. Significant differences in MICs of undissociated lactic acid were found between strains of L. monocytogenes at a given pH, with a maximum observed level of 9.0 mM. Variations in MICs were mostly due to strain variation. In the pH range 5.2-5.6, the MICs of undissociated lactic acid were not significantly different at 12 °C and 30 °C. The average MICs of undissociated acetic acid, citric acid, and propionic acid were 19.0 (SD 6.5) mM, 3.8 (SD 0.9) mM, and 11.0 (SD 6.3) mM, respectively, for the six L. monocytogenes strains tested in the pH range 5.2-5.6. Variations in MICs of these organic acids for L. monocytogenes were also mostly due to strain variation. The generated data contribute to improved predictions of growth/no growth of L. monocytogenes in cheese and other foods containing these organic acids.

  17. Transcriptional deregulation of genetic biomarkers in Chironomus riparius larvae exposed to ecologically relevant concentrations of di(2-ethylhexyl) phthalate (DEHP)

    Morcillo, Gloria; Planelló, Rosario


    Di(2-ethylhexyl) phthalate (DEHP) is a ubiquitous environmental pollutant used worldwide as a plasticizer and solvent in many formulations. Based on available toxicological data, it has been classified as toxic for reproduction and as an endocrine disruptor. Despite this, ecotoxicological studies in aquatic wildlife organisms are still scarce. In the present work, the toxic molecular alterations caused by DEHP in aquatic larvae of the midge Chironomus riparius have been studied, by analyzing the transcriptional activity of genes related to some vital cellular pathways, such as the ribosomal machinery (rpL4, rpL13), the cell stress response (hsc70, hsp70, hsp40, hsp27), the ecdysone hormone pathway (EcR), the energy metabolism (GAPDH), and detoxication processes (CYP4G). Environmentally relevant concentrations (10−3 to 105 μg/L) and exposure conditions (24 to 96 h) have been tested, as well as the toxic effects after DEHP withdrawal. Although the compound caused no mortality, significant changes were detected in almost all the studied biomarkers: e.g. strong repression of hsp70; general inhibition of EcR; GAPDH activity loss in long exposures; among others. Our data show a general transcriptional downregulation that could be associated with an adaptive response to cell damage. Besides, the activity of the compound as an ecdysone antagonist and its delayed effects over almost all the biomarkers analyzed are described as novel toxic targets in insects. PMID:28166271

  18. Salt at concentrations relevant to meat processing enhances Shiga toxin 2 production in Escherichia coli O157:H7.

    Harris, Shaun M; Yue, Wan-Fu; Olsen, Sarena A; Hu, Jia; Means, Warrie J; McCormick, Richard J; Du, Min; Zhu, Mei-Jun


    Escherichia coli (E. coli) O157:H7 remains a major food safety concern associated with meat, especially beef products. Shiga toxins (Stx) are key virulence factors produced by E. coli O157:H7 that are responsible for hemorrhagic colitis and Hemolytic Uremic Syndrome. Stx are heat stable and can be absorbed after oral ingestion. Despite the extensive study of E. coli O157:H7 survival during meat processing, little attention is paid to the production of Stx during meat processing. The objective of this study was to elucidate the effect of salt, an essential additive to processed meat, at concentrations relevant to meat processing (0%, 1%, 2%, 3%, W/V) on Stx2 production and Stx2 prophage induction by E. coli O157:H7 strains. For both E. coli O157:H7 86-24 and EDL933 strains, including 2% salt in LB broth decreased (P<0.05) E. coli O157:H7 population, but increased (P<0.05) Stx2 production (as measured relative to Log(10)CFU) compared to that of the control (1% salt). Supplementing 3% salt decreased (P<0.05) both E. coli O157:H7 number and Stx2 production. Quantitative RT-PCR indicated that stx2 mRNA expression in culture media containing 2% salt was greatly increased (P<0.05) compared to other salt concentrations. Consistent with enhanced Stx2 production and stx2 expression, the 2% salt group had highest lambdoid phage titer and stx2 prophage induction among all salt treatments. RecA is a key mediator of bacterial response to stress, which mediates prophage activation. Quantitative RT-PCR further indicated that recA mRNA expression was higher in both 2% and 3% salt than that of 0% and 1% salt treatments, indicating that stress was involved in enhanced Stx2 production. In conclusion, salt at the concentration used for meat processing enhances Stx production, a process linked to bacterial stress response and lambdoid prophage induction. Published by Elsevier B.V.

  19. Observation on the adverse reactions of different concentrations of povidone-iodine applied before cataract surgery

    Shan-Jun Wu


    Full Text Available AIM: To evaluate the efficiency and safety of 50g/L povidone-iodine solution in preventing postoperative endophthalmitis through comparing the incidence of postoperative endophthalmitis and adverse reactions after conjunctival sac washing with povidone-iodine of different concentrations.METHODS: Totally 500 cataract patients were divided into 50g/L povidone-iodine group and 25g/L povidone-iodine group. All the operated eyes were observed during and after surgery.The patients' subjective discomfort was inquired and their signs of eyes were recorded. RESULTS: The eye irritation of 50g/L povidone-iodine group was more significant than 25g/L povidone-iodine group. No significant difference in the corneal epithelial loss and endophthalmitis was observed between two groups.CONCLUSION:Conjunctival sac washing with 50g/L povidone-iodine is an effective and safe measure to prevent endophthalmitis after cataract surgery.

  20. Effect of platelet rich plasma gel in a physiologically relevant platelet concentration on wounds in persons with spinal cord injury.

    Rappl, Laurie M


    The objective of the study was to investigate the use of a 1·3 times normal platelet concentration platelet-rich plasma (PRP) gel to move chronic wounds towards healing in persons with spinal cord injury (SCI). The study design was a case series of 20 persons with SCI with non healing wounds. The outcome measures were, in wound area, volume, undermining and sinus tracts/tunnels (ST/Ts), calculated average, (i) percent of change from baseline, (ii) change per day from baseline, (iii) number of treatments and (iv) number of weeks. In a mean of 4·0, after treatments over 3·4 weeks, the wounds closed on an average of 47·9% in area and 56·0% in volume. Undermining closed on an average of 31·4% using 3·5 treatments over 2·6 weeks. ST/Ts closed on an average of 26·1% after 2·3 treatments over 1·5 weeks. Clinical relevance by percent of positive responders and their response: in area, 90·0% of the subjects responded positively, the average reduction was 53·8%. In volume, 90·0% responded, with an average reduction of 67·3%. Of four subjects with undermining, 75% closed 47·0% on average. Of the three with ST/Ts, 100% closed 26·1% on average. Average haemoglobin and haematocrit levels were below normal. To conclude, 1·3× PRP gel appears to progress chronic, non healing wounds in SCI patients into the granulation phase of healing quickly. Review of the literature shows these results may not be applied to all PRP preparations.

  1. Chronic wounds treated with a physiologically relevant concentration of platelet-rich plasma gel: a prospective case series.

    Frykberg, Robert G; Driver, Vickie R; Carman, Donna; Lucero, Brenda; Borris-Hale, Cathy; Fylling, Carelyn P; Rappl, Laurie M; Clausen, Peter A


    Chronic wounds are characterized by a long inflammatory phase that hinders regenerative wound healing. The purpose of this prospective case series was to evaluate how a physiologically relevant concentration of an autologous platelet-rich plasma (PRP) gel affects initial wound healing trajectories of chronic, nonhealing wounds of various etiologies and in different care settings. Using convenience sampling methods, 49 patients (average age: 60.6 years, SD 14.7) with 65 nonhealing wounds (mean duration 47.8 weeks, range 3 to 260) at eight long-term acute care (LTAC) hospitals and three outpatient foot or wound clinics who were prescribed PRP gel for their nonhealing wound were enrolled. The majority of patients had low albumin, hematocrit, and/or hemoglobin levels. After wound assessments and measurements were obtained and the gel prepared, a skin barrier was applied to the periwound skin and the gel applied and protected with cover dressings. The most common wounds were pressure ulcers (n = 21), venous ulcers (n = 16) and diabetic foot ulcers (n = 14). Mean wound area and volume were 19 cm2 (SD 29.4) and 36.2 cm3 (SD 77.7), respectively. Following a mean of 2.8 (SD 2.4) weeks with 3.2 (SD 2.2) applications, reductions in wound volume (mean 51%, SD 43.1), area (39.5%, SD 41.2), undermining (77.8%, SD 28.9), and sinus tract/tunneling (45.8%, SD 40.2) were observed. For all wound etiologies, 97% of wounds improved. The results of this study suggest the application of this PRP gel can reverse nonhealing trends in chronic wounds.

  2. Kinetic Analysis of Parallel-Consecutive First-Order Reactions with a Reversible Step: Concentration-Time Integrals Method

    Mucientes, A. E.; de la Pena, M. A.


    The concentration-time integrals method has been used to solve kinetic equations of parallel-consecutive first-order reactions with a reversible step. This method involves the determination of the area under the curve for the concentration of a given species against time. Computer techniques are used to integrate experimental curves and the method…

  3. Alcohol-to-acid ratio and substrate concentration affect product structure in chain elongation reactions initiated by unacclimatized inoculum.

    Liu, Yuhao; Lü, Fan; Shao, Liming; He, Pinjing


    The objective of the study was to investigate whether the ratio of ethanol to acetate affects yield and product structure in chain elongation initiated by unacclimatized mixed cultures. The effect of varying the substrate concentration, while maintaining the same ratio of alcohol to acid, was also investigated. With a high substrate concentration, an alcohol to acid ratio >2:1 provided sufficient electron donor capacity for the chain elongation reaction. With an ethanol to acetate ratio of 3:1 (300mM total carbon), the highest n-caproate concentration (3033±98mg/L) was achieved during the stable phase of the reaction. A lower substrate concentration (150mM total carbon) gave a lower yield of products and led to reduced carbon transformation efficiency compared with other reaction conditions. The use of unacclimatized inoculum in chain elongation can produce significant amounts of odd-carbon-number carboxylates as a result of protein hydrolysis.

  4. Experimental Study on Surface Reactions of Heavy Metal Ions With Quartz—Aqueous Ion Concentration Dependence

    吴宏海; 吴大清; 等


    Adsorption of divalent metal ions,including Cu2+,Pb2+,Zn2+,Cd2+ and Ni2+,on quartz surface was measured as a function of metal ion concentration at 30℃under condi tions of solution pH=6.5 and ion strength I=0.1mol/L.Results of the experimental measuements can be described very well by adsorption isoterm dquations of Freudlich.The correlation coefficients(r)of adsorption isotherm lines are>0.96.Moreover,the exprimental data were interpreted on the basis of surface complexation model.Te experimental results showed that the monodentate-coordinated metal ion surface complex species(SOM+)are predominant over the bidentate-coordinated metal ion surface complex species[(SO)2M]formed only by the ions Cu2+,Zn2+ and Ni2+,And the relevant apparent surface complexation constants are lgKM=2.2-3.3 in order of KCd≥KPb>KZn>KNi≥KCu,and lgβM=5.8-6.8 in oder of βNi>βZn>βCu.Therefore,the reactive ability of the ions onto mineral surface of quartz follows the order of Cd>Pb>Zn>Ni>Cu under the above-mentioned solution conditions.The apparent surface complexation constants,influenced by the surface potential,surface species and hydrolysis of metal ions,depend mainly on the Born solvation coefficeient of the metal ions.

  5. Experimental studies of keV energy neutron-induced reactions relevant to astrophysics and nuclear physics

    Shima, T.; Kii, T.; Kikuchi, T.; Okazaki, F.; Kobayashi, T.; Baba, T.; Nagai, Y. [Tokyo Inst. of Tech. (Japan). Faculty of Science; Igashira, M.


    Nuclear reactions induced by keV energy neutrons provide a plenty of informations for studies of both astrophysics and nuclear physics. In this paper we will show our experimental studies of neutron- induced reactions of light nuclei in the keV energy region by means of a pulsed keV neutron beam and high-sensitivity detectors. Also we will discuss astrophysical and nuclear-physical consequences by using the obtained results. (author)

  6. Theoretical uncertainty of (α ,n ) reactions relevant for the nucleosynthesis of light r -process nuclei in neutrino-driven winds

    Pereira, J.; Montes, F.


    Background: Neutrino-driven winds following core-collapse supernova explosions have been proposed as a possible site where light r -process nuclei (between Fe and Ag) might be synthesized. In these events, (α ,n ) reactions are key to moving matter towards the region of higher proton number. Abundance network calculations are very sensitive to the rates for this type of reactions. Purpose: The present work aims at evaluating the theoretical uncertainty of these (α ,n ) reactions calculated with reaction codes based on the Hauser-Feshbach model. Method: We compared several (α ,n ) rates taken from talys and the non-smoker database to determine the uncertainties owing to the existing technical differences between both codes. In addition, we evaluated the sensitivity of talys rates to variations in the α optical potentials, masses, level densities, optical potentials, preequilibrium intranuclear transition rates, level structure, radiative transmission coefficients, and width-fluctuation correction factors. Results: The main source of uncertainty at low temperature is mostly attributable to the use of different α optical potentials. Differences between talys and non-smoker at high temperatures arise from the energy-binning algorithm used by each code. We have also noticed that the (α ,n ) rates from the non-smoker database correspond to the inclusive reaction, instead of the exclusive (α ,1 n ) channel calculated in the present work and used in network calculations. Conclusions: Theoretical uncertainties in calculated reaction rates can be as high as one to two orders of magnitude and strongly dependent on the temperature of the environment. Besides direct measurements of the inclusive and exclusive (α ,1 n ) reaction rates, experimental studies of α optical potentials are crucial to improve the performance of reaction codes.

  7. A theoretical study of the mechanism of the atmospherically relevant reaction of chlorine atoms with methyl nitrate, and calculation of the reaction rate coefficients at temperatures relevant to the troposphere.

    Ng, Maggie; Mok, Daniel K W; Lee, Edmond P F; Dyke, John M


    The reaction between atomic chlorine (Cl) and methyl nitrate (CH3ONO2) is significant in the atmosphere, as Cl is a key oxidant, especially in the marine boundary layer, and alkyl nitrates are important nitrogen-containing organic compounds, which are temporary reservoirs of the reactive nitrogen oxides NO, NO2 and NO3 (NOx). Four reaction channels HCl + CH2ONO2, CH3OCl + NO2, CH3Cl + NO3 and CH3O + ClNO2 were considered. The major channel is found to be the H abstraction channel, to give the products HCl + CH2ONO2. For all channels, geometry optimization and frequency calculations were carried out at the M06-2X/6-31+G** level, while relative electronic energies were improved to the UCCSD(T*)-F12/CBS level. The reaction barrier (ΔE(‡)0K) and reaction enthalpy (ΔH(RX)298K) of the H abstraction channel were computed to be 0.61 and -2.30 kcal mol(-1), respectively, at the UCCSD(T*)-F12/CBS//M06-2X/6-31+G** level. Reaction barriers (ΔE(‡)0K) for the other channels are more positive and these pathways do not contribute to the overall reaction rate coefficient in the temperature range considered (200-400 K). Rate coefficients were calculated for the H-abstraction channel at various levels of variational transition state theory (VTST) including tunnelling. Recommended ICVT/SCT rate coefficients in the temperature range 200-400 K are presented for the first time for this reaction. The values obtained in the 200-300 K region are particularly important as they will be valuable for atmospheric modelling calculations involving reactions with methyl nitrate. The implications of the results to atmospheric chemistry are discussed. Also, the enthalpies of formation, ΔHf,298K, of CH3ONO2 and CH2ONO2 were computed to be -29.7 and 19.3 kcal mol(-1), respectively, at the UCCSD(T*)-F12/CBS level.

  8. Shielding effects in polymer-polymer reactions. V. Concentration dependence of contact formation between star-branched and linear chains.

    Nardai, Michael M; Zifferer, Gerhard


    By use of the Dissipative Particle Dynamics (DPD) simulation technique mixtures of star-branched (arm number F = 4) and linear chains in athermal (good) solvent are analyzed regarding probabilities for intermolecular contacts of various reactive sites within different polymer coils. The accompanying sterical hindrances are described in the framework of shielding factors in order to investigate reactions and side reactions in radical polymerization and other techniques that involve polymer-polymer coupling. The shielding factors are studied as a function of total concentration from high dilution up to the bulk for different chain lengths of star-shaped and linear chains. Results indicate that their concentration dependence can be described by a power law for systems above the overlap concentration, whereas the chain length dependence vanishes when extrapolating to infinite chain lengths in that concentration range. Also the influence of the ratio of star chains and linear chains is studied for various concentrations.

  9. First Measurement of the 19F(α, p)22Ne Reaction at Energies of Astrophysical Relevance

    Pizzone, R. G.; D’Agata, G.; La Cognata, M.; Indelicato, I.; Spitaleri, C.; Blagus, S.; Cherubini, S.; Figuera, P.; Grassi, L.; Guardo, G. L.; Gulino, M.; Hayakawa, S.; Kshetri, R.; Lamia, L.; Lattuada, M.; Mijatović, T.; Milin, M.; Miljanić D., Đ.; Prepolec, L.; Rapisarda, G. G.; Romano, S.; Sergi, M. L.; Skukan, N.; Soić, N.; Tokić, V.; Tumino, A.; Uroić, M.


    The observational 19F abundance in stellar environments systematically exceeds the predicted one, thus representing one of the unsolved challenges for stellar modeling. It is therefore clear that further investigation is needed in this field. In this work, we focus our attention on the measurement of the {}19{{F}}{(α ,p)}22{Ne} reaction in the astrophysical energy range, between 0.2 and 0.8 MeV (far below the Coulomb barrier, 3.8 MeV), as it represents the main destruction channel in He-rich environments. The lowest energy at which this reaction has been studied with direct measurements is ∼0.66 MeV, covering only the upper tail of the Gamow window, causing the reaction-rate evaluation to be based on extrapolation. To investigate lower energies, the {}19{{F}}{(α ,p)}22{Ne} reaction has been studied by means of the Trojan horse method, applied to the quasi-free {}6{Li}{{(}19{{F}},{p}22{Ne})}2{{H}} reaction at E beam = 6 MeV. The indirect cross section of the {}19{{F}}{(α ,p)}22{Ne} reaction at energies ≲1 MeV was extracted, fully covering the astrophysical region of interest and overlapping existing direct data for normalization. Several resonances have been detected for the first time inside the Gamow window. The reaction rate has been calculated, showing an increase up to a factor of 4 with respect to the literature at astrophysical temperatures. This might lead to potential major astrophysical implications.

  10. Kinetics of the glucose/glycine Maillard reaction pathways: influences of pH and reactant initial concentrations

    Martins, S.I.F.S.; Boekel, van M.A.J.S.


    A previously proposed kinetic model for the glucose/glycine Maillard reaction pathways has been validated by changing the initial pH (4.8, 5.5, 6.0, 6.8 and 7.5) of the reaction and reactant initial concentrations (1:2 and 2:1 molar ratios were compared to the 1:1 ratio). The model consists of 10

  11. Reactions of potent antitumor complex trans-[Ru(III)Cl4(indazole)2]- with a DNA-relevant nucleobase and thioethers: insight into biological action.

    Egger, Alexander; Arion, Vladimir B; Reisner, Erwin; Cebrián-Losantos, Berta; Shova, Sergiu; Trettenhahn, Günter; Keppler, Bernhard K


    Reactions of the complex trans-[RuCl(4)(Hind)(2)](-) (Hind = indazole), which is of clinical relevance today, with both the DNA model nucleobase 9-methyladenine (made) and the thioethers R(2)S (R = Me, Et), as models of the methionine residue in biological molecules possibly acting as nitrogen-competing sulfur-donor ligands for ruthenium atom, have been investigated to get insight into details of mechanism leading to antitumor activity. Three novel ruthenium complexes, viz., [Ru(III)Cl(3)(Hind)(2)(made)], 1, [Ru(II)Cl(2)(Hind)(2)(Me(2)S)(2)], 2, and [Ru(II)Cl(2)(Hind)(2)(Et(2)S)(2)], 3, have been isolated as solids. Oxidation of 2 and 3 with hydrogen peroxide in the presence of 12 M HCl in chloroform afforded the monothioether adducts, viz., [Ru(III)Cl(3)(Hind)(2)(Me(2)S)], 4, and [Ru(III)Cl(3)(Hind)(2)(Et(2)S)], 5. By dissolution of 2 or 3 in DMSO, replacement of both R(2)S ligands by DMSO molecules occurred with isolation of trans,trans,trans-[Ru(II)Cl(2)(Hind)(2)(DMSO)(2)], 6. The products were characterized by elemental analysis, IR, UV-vis, electrospray mass spectrometry, cyclic voltammetry, and X-ray crystallography (1.CH(2)Cl(2).CH(3)OH and 1.1.1H(2)O.0.9CH(3)OH, 2, and 5). The first crystallographic evidence for the monofunctional coordination of the 9-methyladenine ligand to ruthenium via N7 and the self-pairing of the complex molecules via H-bonding, using the usual Watson-Crick pairing donor and acceptor sites of two adjacent 9-methyladenine ligands, is reported. The electrochemical behavior of 1-5 has been studied in DMF and DMSO by cyclic voltammetry. The redox potential values have been interpreted on the basis of the Lever's parametrization method. The E(L) parameter was estimated for 9-methyladenine at 0.18 V, showing that this ligand behaves as a weaker net electron donor than imidazole (E(L) = 0.12 V). The kinetics of the reductively induced stepwise replacement of chlorides by DMF in 4 and 5 were studied by digital simulation of the cyclic

  12. A Modified activation method for reaction total cross section and yield measurements at low astrophysically relevant energies

    Artemov, S.V., E-mail: [Institute of Nuclear Physics of Uzbekistan Academy of Sciences, Tashkent (Uzbekistan); Igamov, S.B.; Karakhodjaev, A.A.; Radyuk, G.A.; Tojiboyev, O.R.; Salikhbaev, U.S.; Ergashev, F.Kh.; Nam, I.V. [Institute of Nuclear Physics of Uzbekistan Academy of Sciences, Tashkent (Uzbekistan); Aliev, M.K.; Kholbaev, I.; Rumi, R.F.; Khalikov, R.I.; Eshkobilov, Sh.Kh.; Muminov, T.M. [Research Institute of Applied Physics, National University of Uzbekistan, Tashkent (Uzbekistan)


    The activation method is proposed for collection of the sufficient statistics during the investigation of the nuclear astrophysical reactions at low energies with the short-living residual nuclei formation. The main feature is a multiple cyclical irradiation of a target by an ion beam and measurement of the radioactivity decay curve. The method was tested by the yield measurement of the {sup 12}C(p,γ){sup 13}N reaction with detecting the annihilation γγ- coincidences from {sup 13}N(β{sup +}ν){sup 13}C decay at the two-arm scintillation spectrometer.

  13. Measurement of the $^{44}$Ti($\\alpha$,p)$^{47}$V reaction cross section, of relevance to $\\gamma$-ray observation of core collapse supernovae, using reclaimed $^{44}$Ti

    Despite decades of research, fundamental uncertainties remain in the underlying explosion mechanism of core collapse supernovae. One of the most direct methods that might help resolve this problem is a comparison of the predicted to the observed flux of $\\gamma$-rays due to decay of $^{44}$Ti produced in the explosion, as it is believed this could reveal the location of the mass cut, a key hydrodynamical property of the explosion. Such a study is at present limited by the uncertainty in the $^{44}$Ti($\\alpha$,p)$^{47}$V reaction rate. In this experiment we propose to measure the cross section for this reaction at astrophysically relevant energies. The single previous measurement of this reaction was limited to higher energies due to low beam intensities. Here, a more intense beam will be employed, generated from $^{44}$Ti reclaimed as part of the ERAWAST project at PSI.

  14. A VUV photoionization study of the multichannel reaction of phenyl radicals with 1,3-butadiene under combustion relevant conditions.

    Golan, Amir; Ahmed, Musahid; Mebel, Alexander M; Kaiser, Ralf I


    We studied the reaction of phenyl radicals (C(6)H(5)) with 1,3-butadiene (H(2)CCHCHCH(2)) exploiting a high temperature chemical reactor under combustion-like conditions (300 Torr, 873 K). The reaction products were probed in a supersonic beam by utilizing VUV radiation from the Advanced Light Source and by recording the experimental PIE curves at mass-to-charge ratios of m/z = 130 (C(10)H(10)(+)), 116 (C(9)H(8)(+)), and 104 (C(8)H(8)(+)). Our data suggest that the atomic hydrogen (H), methyl (CH(3)), and vinyl (C(2)H(3)) losses are open with estimated branching ratios of about 86 ± 4%, 8 ± 2%, and 6 ± 2%, respectively. The isomer distributions were probed further by fitting the experimentally recorded PIE curves with a linear combination of the PIE curves of individual C(10)H(10), C(9)H(8), and C(8)H(8) isomers. These fits indicate the formation of three C(10)H(10) isomers (trans-1,3-butadienylbenzene, 1,4-dihydronaphthalene, 1-methylindene), three C(9)H(8) isomers (indene, phenylallene, 1-phenyl-1-methylacetylene), and a C(8)H(8) isomer (styrene). A comparison with results from recent crossed molecular beam studies of the 1,3-butadiene-phenyl radical reaction and electronic structure calculations suggests that trans-1,3-butadienylbenzene (130 amu), 1,4-dihydronaphthalene (130 amu), and styrene (104 amu) are reaction products formed as a consequence of a bimolecular reaction between the phenyl radical and 1,3-butadiene. 1-Methylindene (130 amu), indene (116 amu), phenylallene (116 amu), and 1-phenyl-1-methylacetylene (116 amu) are synthesized upon reaction of the phenyl radical with three C(4)H(6) isomers: 1,2-butadiene (H(2)CCCH(CH(3))), 1-butyne (HCCC(2)H(5)), and 2-butyne (CH(3)CCCH(3)); these C(4)H(6) isomers can be formed from 1,3-butadiene via hydrogen atom assisted isomerization reactions or via thermal rearrangements of 1,3-butadiene involving hydrogen shifts in the high temperature chemical reactor.

  15. Investigation Into Accessible Surface Vinyl Concentrations of Nonstoichiometric PDMS Microspheres from Hydrosilylation Reactions and Their Further Crosslinking Reactions

    Ma, Baoguang; Hansen, Jens Henrik; Hvilsted, Søren;


    titration method, which is based on efficiently and covalently bonding mono-functional hydride to vinyl, is employed to determine surface vinyl concentration. The titration method exhibits good reproducibility in detection, thereby underlining its potential applicability as a general titration method...... for cured silicones. Vinyl functional PDMS microspheres are mixed with a hydride crosslinker and non-reactive silicone oil to create a system which allows for extensive crosslinking. Both visual observations and rheological studies show that a robust macroscopic PDMS elastomer is obtained upon crosslinking...

  16. Driving impairment due to propofol at effect-site concentrations relevant after short propofol-only sedation.

    Telles, J L; Agarwal, S; Monagle, J; Stough, C; King, R; Downey, L


    Australian guidelines state "Following brief surgery or procedures with short acting anaesthetic drugs, the patient may be fit to drive after a normal night's sleep. After long surgery or procedures requiring longer lasting anaesthesia, it may not be safe to drive for 24 hours or more". The increasing use of the short-acting anaesthetic drug propofol as a solitary sedative medication for simple endoscopy procedures suggests a need to review this blanket policy. Thirty patients presenting for elective day surgery were recruited as volunteers for a pre-procedure driving simulation study and randomised to propofol or placebo arms. Driving ability was assessed at baseline and then, in the propofol group, at three effect-site concentrations. Driving impairment at these concentrations of propofol was compared to that of a third group of volunteers with a blood alcohol concentration of 0.05% (g/100 ml). Driving impairment at 0.2 µg/ml propofol effect-site concentration was not statistically different to placebo. Impairment increased with propofol effect-site concentration (P=0.002) and at 0.4 µg/ml it was similar to that found with a blood alcohol concentration of 50 mg/100 ml (0.05%). Plasma propofol concentrations of 0.2 µg/ml, as might be found approximately an hour after short (propofol-only sedation for endoscopy, were not associated with driving impairment in our young cohort of volunteers.

  17. Toxic effects of lead on biochemical and histological alterations in green mussel (Perna viridis) induced by environmentally relevant concentrations.

    Hariharan, G; Purvaja, R; Ramesh, R


    Acute and chronic toxicity tests were conducted on green mussel (Perna viridis) to determine the adverse effects of lead (Pb). Exposure of organisms to acute toxicity test for 96 h and lethal concentration (LC(50)) was the endpoint of the test. Acute toxicity for 96-h LC(50) and 95% confidence intervals of P. viridis was 2.62 ± 0.12 (2.62-3.24) mg/L Pb. Chronic toxicity tests revealed that survival of exposed organisms decreased with elevated exposure concentrations. No-observed-effect concentration (NOEC) and lowest-observed-effect concentration (LOEC) were calculated based on survival of test organisms. Results of this study demonstrated an increase in toxicity in test organisms with rise in exposure time and concentration. In this study, histology and biochemical enzymes, namely, catalase, reduced glutathione, glutathione S-transferase, and lipid peroxides, were correlated with chronic value and survival endpoints of P. viridis after chronic exposure to Pb. Biochemical and histological responses to different concentrations of Pb were assessed and significant differences were observed between control and increasing exposure concentrations. Biomarker studies in internal organs confirmed that the observed changes are due to adverse effects of Pb. This assessment of toxicity was the first step to determining the seawater quality criteria for marine organisms.

  18. Concentration fluctuations in non-isothermal reaction-diffusion systems. II. The nonlinear case

    Bedeaux, D.; Ortiz de Zárate, J.M.; Pagonabarraga, I.; Sengers, J.V.; Kjelstrup, S.


    In this paper, we consider a simple reaction-diffusion system, namely, a binary fluid mixture with an association-dissociation reaction between two species. We study fluctuations at hydrodynamic spatiotemporal scales when this mixture is driven out of equilibrium by the presence of a temperature gra

  19. A combined experimental and theoretical study of reactions between the hydroxyl radical and oxygenated hydrocarbons relevant to astrochemical environments.

    Shannon, R J; Caravan, R L; Blitz, M A; Heard, D E


    The kinetics of the reactions of the hydroxyl radical (OH) with acetone and dimethyl ether (DME) have been studied between 63-148 K and at a range of pressures using laser-flash photolysis coupled with laser induced fluorescence detection of OH in a pulsed Laval nozzle apparatus. For acetone, a large negative temperature dependence was observed, with the rate coefficient increasing from k1 = (1.6 ± 0.8) × 10(-12) cm(3) molecule(-1) s(-1) at 148 K to (1.0 ± 0.1) × 10(-10) cm(3) molecule(-1) s(-1) at 79 K, and also increasing with pressure. For DME, a similar behaviour was found, with the rate coefficient increasing from k2 = (3.1 ± 0.5) × 10(-12) cm(3) molecule(-1) s(-1) at 138 K to (1.7 ± 0.1) × 10(-11) cm(3) molecule(-1) s(-1) at 63 K, and also increasing with pressure. The temperature and pressure dependence of the experimental rate coefficients are rationalised for both reactions by the formation and subsequent stabilisation of a hydrogen bonded complex, with a non-zero rate coefficient extrapolated to zero pressure supportive of quantum mechanical tunnelling on the timescale of the experiments leading to products. In the case of DME, experiments performed in the presence of O2 provide additional evidence that the yield of the CH3OCH2 abstraction product, which can recycle OH in the presence of O2, is ≥50%. The experimental data are modelled using the MESMER (Master Equation Solver for Multi Energy Well Reactions) code which includes a treatment of quantum mechanical tunnelling, and uses energies and structures of transition states and complexes calculated by ab initio methods. Good agreement is seen between experiment and theory, with MESMER being able to reproduce for both reactions the temperature behaviour between ~70-800 K and the pressure dependence observed at ~80 K. At the limit of zero pressure, the model predicts a rate coefficient of ~10(-11) cm(3) molecule(-1) s(-1) for the reaction of OH with acetone at 20 K, providing evidence that the

  20. Investigation Into Accessible Surface Vinyl Concentrations of Nonstoichiometric PDMS Microspheres from Hydrosilylation Reactions and Their Further Crosslinking Reactions

    Ma, Baoguang; Hansen, Jens Henrik; Hvilsted, Søren


    The introduction of surface vinyl groups to PDMS microspheres broadens the latter's applicability range since the microspheres can be further functionalized or crosslinked into elastomers. Quantification of the surface vinyl concentration of PDMS microspheres is therefore essential. Here, a novel...... for cured silicones. Vinyl functional PDMS microspheres are mixed with a hydride crosslinker and non-reactive silicone oil to create a system which allows for extensive crosslinking. Both visual observations and rheological studies show that a robust macroscopic PDMS elastomer is obtained upon crosslinking....... Furthermore, the influence of stoichiometric imbalance, and the weight fraction of silicone oil on the terminal storage modulus of the macroscopic PDMS elastomer, is investigated. The wide range of stoichiometries facilitating crosslinking between the PDMS microspheres and the hydride crosslinker found...

  1. Environmentally relevant concentrations of ammonium perchlorate inhibit thyroid function and alter sex ratios in developing Xenopus laevis.

    Goleman, Wanda L; Carr, James A; Anderson, Todd A


    Embryos and larvae of the South African frog Xenopus laevis were exposed to ammonium perchlorate (AP) or control medium for 70 d. The dosage levels (59 ppb, 14,140 ppb) bracketed a range of perchlorate concentrations measured in surface waters at the Longhorn Army Ammunition Plant (LHAAP) in Karnack, Texas, USA. The experiment also included a 28-d nontreatment recovery period to assess the reversibility of AP effects. There were no significant effects of AP on mortality or hatching success. There were no effects of AP on developmental abnormalities such as bent/asymmetric tails or edema. Ammonium perchlorate inhibited forelimb emergence, the percentage of animals completing tail resorption, and hindlimb development during the 70-d exposure period. Only the upper AP concentration reduced whole-body thyroxine content, whereas both concentrations caused significant hypertrophy of the thyroid follicular epithelium. Both concentrations of AP caused a skewed sex ratio, significantly reducing the percentage of males at metamorphosis. The effects of AP on metamorphosis and thyroid function were reversed during the 28-d nontreatment recovery period. We conclude that AP inhibits thyroid activity and alters gonadal differentiation in developing X. laevis. These effects were observed at concentrations at or below concentrations reported in surface waters contaminated with ammonium perchlorate, suggesting that this contaminant may pose a threat to normal development and growth in natural amphibian populations.

  2. The H2 + CO ↔ H2CO Reaction: Rate Constants and Relevance to Hot and Dense Astrophysical Media

    Vichietti, R. M.; Spada, R. F. K.; da Silva, A. B. F.; Machado, F. B. C.; Haiduke, R. L. A.


    A theoretical thermochemical and kinetic investigation of the thermal H2 + CO ↔ H2CO reaction was performed for a temperature range from 200 to 4000 K. Geometries and vibrational frequencies of reactants, product, and transition state (TS) were obtained at CCSD/cc-pVxZ (x = T and Q) levels and scaling factors were employed to consider anharmonicity effects on vibrational frequencies, zero-point energies, and thermal corrections provided by these methodologies. Enthalpies Gibbs energies, and rate constants for this reaction were determined by including a complete basis set extrapolation correction for the electronic properties calculated at CCSD(T)/cc-pVyZ (y = Q and 5) levels. Our study indicates that enthalpy changes for this reaction are highly dependent on temperature. Moreover, forward and reverse (high-pressure limit) rate constants were obtained from variational TS theory with quantum tunneling corrections. Thus, modified Arrhenius’ equations were fitted by means of the best forward and reverse rate constant values, which provide very reliable estimates for these quantities within the temperature range between 700 and 4000 K. To our knowledge, this is the first kinetic study done for the forward H2 + CO \\to H2CO process in a wide temperature range. Finally, these results can be used to explain the formaldehyde abundance in hot and dense interstellar media, possibly providing data about the physical conditions associated with H2CO masers close to massive star-forming regions.

  3. Carboxylic acid functionalization prevents the translocation of multi-walled carbon nanotubes at predicted environmentally relevant concentrations into targeted organs of nematode Caenorhabditis elegans

    Nouara, Abdelli; Wu, Qiuli; Li, Yinxia; Tang, Meng; Wang, Haifang; Zhao, Yuliang; Wang, Dayong


    Carboxyl (-COOH) surface modified multi-walled carbon nanotubes (MWCNTs-COOH) can be used for targeted delivery of drugs and imaging. However, whether MWCNTs-COOH at environmentally relevant concentrations exert certain toxic effects on multicellular organisms and the underlying mechanisms are still largely unclear. In the present study, we applied the nematode Caenorhabditis elegans to evaluate the properties of MWCNTs-COOH at environmentally relevant concentrations by comparing the effects of MWCNTs and MWCNTs-COOH exposure on C. elegans from L1-larvae to adult at concentrations of 0.001-1000 μg L-1. Exposure to MWCNTs could potentially damage the intestine (primary targeted organ) at concentrations greater than 0.1 μg L-1 and functions of neurons and reproductive organ (secondary targeted organs) at concentrations greater than 0.001 μg L-1. Carboxyl modification prevented the toxicity of MWCNTs on the primary and the secondary targeted organs at concentrations less than 100 μg L-1, suggesting that carboxyl modification can effectively prevent the adverse effects of MWCNTs at environmentally relevant concentrations. After exposure, MWCNTs-COOH (1 mg L-1) were translocated into the spermatheca and embryos in the body through the primary targeted organs. However, MWCNTs-COOH (10 μg L-1) were not observed in spermatheca and embryos in the body of nematodes. Moreover, relatively high concentrations of MWCNTs-COOH exposed nematodes might have a hyper-permeable intestinal barrier, whereas MWCNTs-COOH at environmentally relevant concentrations effectively sustained the normally permeable state for the intestinal barrier. Therefore, we elucidated the cellular basis of carboxyl modification to prevent toxicity of MWCNTs at environmentally relevant concentrations. Our data highlights the key role of biological barriers in the primary targeted organs to block toxicity formation from MWCNTs, which will be useful for the design of effective prevention strategies against

  4. Relevance of dietary protein concentration and quality as risk factors for the formation of calcium oxalate stones in cats.

    Paßlack, Nadine; Burmeier, Hannes; Brenten, Thomas; Neumann, Konrad; Zentek, Jürgen


    The role of dietary protein for the development of feline calcium oxalate (CaOx) uroliths has not been conclusively clarified. The present study evaluated the effects of a varying dietary protein concentration and quality on critical indices for the formation of CaOx uroliths. Three diets with a high protein quality (10-11 % greaves meal/diet) and a varying crude protein (CP) concentration (35, 44 and 57 % in DM) were compared. Additionally, the 57 % CP diet was compared with a fourth diet that had a similar CP concentration (55 % in DM), but a lower protein quality (34 % greaves meal/diet). The Ca and oxalate (Ox) concentrations were similar in all diets. A group of eight cats received the same diet at the same time. Each feeding period was divided into a 21 d adaptation period and a 7 d sampling period to collect urine. There were increases in urinary volume, urinary Ca concentrations, renal Ca and Ox excretion and urinary relative supersaturation (RSS) with CaOx with increasing dietary protein concentrations. Urinary pH ranged between 6·34 and 6·66 among all groups, with no unidirectional effect of dietary protein. Lower renal Ca excretion was observed when feeding the diet with the lower protein quality, however, the underlying mechanism needs further evaluation. In conclusion, although the observed higher urinary volume is beneficial, the increase in urinary Ca concentrations, renal Ca and Ox excretion and urinary RSS CaOx associated with a high-protein diet may be critical for the development of CaOx uroliths in cats.

  5. Valence shell charge concentration (VSCC) evolution: a tool to investigate the transformations within a VSCC throughout a chemical reaction.

    Cortés-Guzmán, Fernando; Gómez, Rosa María; Rocha-Rinza, Tomas; Sánchez-Obregón, María Azucena; Guevara-Vela, José Manuel


    Theoretical studies about reaction mechanisms are usually limited to the determination of the energetic paths that connect reactants, transition states, and products. Recently, our group proposed the structural evolution, which has provided insights about the molecular structure changes occurring along a reaction path. Structural evolution may be defined as the development of a chemical reaction system across the partitioning of the nuclear configuration space into a finite number of structural regions defined on account of the topology of a scalar field, e.g., the electron density. In this paper, we present a tool to investigate within the framework of the Quantum Theory of Atoms in Molecules the evolvement of the Valence Shell Charge Concentration, the VSCC evolution, which is the description of the changes of electron density concentrations and depletions around the bonding area of an atom. The VSCC evolution provides supplementary information to the structural evolution because it allows the analysis of valence shells within a structural region, i.e., a subset of R(Q) with the same connectivity among the atoms forming a molecule. This new approach constitutes also a complement to the Valence-Shell Electron Pair Repulsion (VSEPR) model because it gives an account of the adjustments of electron pairs in the valence shell of an atom across a chemical reaction. The insertion reaction in the hydroformylation reaction of ethylene, the reduction of cyclohexanone with lithium aluminum hydride, the oxidation of methanol with chlorochromate, and the bimolecular nucleophilic substitution of CH(3)F with F(-) are used as representatives examples of the application of the VSCC evolution. Overall, this paper shows how the VSCC evolution through an analysis of the modifications of local charge concentrations and depletions in individual steps of a chemical reaction gives new insights about these processes.

  6. Crossed beam investigation of elementary reactions relevant to the formation of polycyclic aromatic hydrocarbon (PAH)-like molecules in extraterrestrial environments

    Kaiser, R. I.; Asvany, O.; Lee, Y. T.


    The reactions of ground state carbon atoms, C( 3P j), with benzene, C 6H 6, and phenyl radicals, C 6H 5, with methylacetylene, CH 3CCH, were investigated in crossed beam experiments at collision energies of 21.8 and 140 kJ mol -1 to investigate elementary reactions relevant to the formation and chemistry of polycyclic aromatic hydrocarbons (PAHs) in extraterrestrial environments. The C( 3P j) reaction proceeds via complex formation and gives a cyclic, seven-membered C 7H 5 doublet radical plus atomic hydrogen. This pathway has neither an entrance nor exit barrier, and is exothermic. Together with the experimental verification of the carbon versus hydrogen exchange under single collision conditions, the findings have an important impact on the chemistry of aromatic molecules in interstellar clouds and outflow of carbon stars. Even in the coldest molecular clouds ( T=10 K), the benzene molecule can be destroyed upon reaction with carbon atoms, whereas they are resistant toward an attack of oxygen and nitrogen atoms. Since the aromatic benzene unit is ubiquitous in extraterrestrial, PAH-like material, our results suggest that PAHs might react with carbon atoms as well. On the other side, the reaction of C 6H 5 radicals with methylacetylene to form phenylmethylacetylene is direct. Since an entrance barrier inhibits the reaction in cold molecular clouds and in the atmospheres of hydrocarbon rich planets like Jupiter and Saturn and satellites such as Titan, this reaction is expected to play a role in PAH synthesis only in high temperature interstellar environments, such as circumstellar outflows of carbon stars.

  7. Analysis of armature reaction and winding inductances of permanent magnet brushless DC motor with deep slot concentrated coils

    HUANG Ping-lin; HU Qian-sheng; YU Li; HUANG Yun-kai


    Based on the configuration of deep slot concentrated coils,an analytical model is developed for predicting the armature reaction field produced by the 3-phase stator windings of permanent magnet brushless DC motors with concentrated coils by using the image method and the analytical functions of the armature reaction and winding inductances are proposed accounting for the influence of statot slotting.This approach is different from the method of equivalent distributed current sheet and more suitable for electric machines,which have concentrated coils and deeper slots.Under different control mode,the different analytical functions are presented.This will be helpful when further analyzing the performance of the motor.The results agree with the experiment very well.

  8. Response of phytochelatins and their relationship with cadmium toxicity in a floating macrophyte Pistia stratiotes L. at environmentally relevant concentrations.

    Wang, C; Wang, L Y; Sun, Q


    An indoor experiment was undertaken to investigate the response of phytochelatins and their relationship to cadmium toxicity in Pistia stratiotes L., a free-floating macrophyte, exposed to low concentrations of cadmium typically found in realistic environments. Cadmium concentrations of 0.01 to 0.08 microM had no toxic effects on the growth of this plant, as indicated by no significant changes in the fresh weights of leaves and roots and the slight induction of phytochelatins in plant tissues, whereas cadmium concentrations of 0.16 to 1 microM were toxic, and cadmium toxicity increased with the increase of cadmium concentrations in solutions, accompanied by the dramatic production of phytochelatins in plant tissues, especially in roots. There was a positive correction between root phytochelatin levels and cadmium toxicity, as measured by the growth inhibition rate of the root fresh weight. The results suggested that phytochelatins in aquatic macrophytes can serve as sensitive biomarkers for heavy metal toxicity in a moderately polluted water environment.

  9. An Investigation into the Impact of Reaction Temperature on Various Parameters during Torrefaction of Sugarcane Bagasse Relevant to Gasification

    Anthony Anukam


    Full Text Available Torrefaction of sugarcane bagasse was conducted in an electric muffle furnace at 200, 250, and 300°C in order to establish the impact of heat treatment temperature on various parameters and as a method to improve sugarcane bagasse characteristics for the purpose of gasification. The results show that weight loss of bagasse reduced as temperature of torrefaction increased due to excessive devolatilization. A reduced moisture and volatile matter content as well as improved calorific value were also achieved with increasing temperature of torrefaction. The torrefaction progress was again followed by elemental analysis of the material which showed the presence of C, H, and O in varying proportions depending on torrefaction temperature. The decrease in the weight percentages of O2 and H2 as torrefaction reaction temperature increased resulted in the accumulation of C in the solid product. The thermogravimetric analysis conducted established the maximum reactivity temperature of the torrefied material and revealed that the degradation of torrefied sugarcane bagasse was accelerated by thermal treatment of the material prior to analysis. Finally, the study established that torrefaction at 300°C led to a much more degraded material compared to the lower torrefaction reaction temperatures of 200 and 250°C, respectively.

  10. Simulation of reaction diffusion processes over biologically relevant size and time scales using multi-GPU workstations.

    Hallock, Michael J; Stone, John E; Roberts, Elijah; Fry, Corey; Luthey-Schulten, Zaida


    Simulation of in vivo cellular processes with the reaction-diffusion master equation (RDME) is a computationally expensive task. Our previous software enabled simulation of inhomogeneous biochemical systems for small bacteria over long time scales using the MPD-RDME method on a single GPU. Simulations of larger eukaryotic systems exceed the on-board memory capacity of individual GPUs, and long time simulations of modest-sized cells such as yeast are impractical on a single GPU. We present a new multi-GPU parallel implementation of the MPD-RDME method based on a spatial decomposition approach that supports dynamic load balancing for workstations containing GPUs of varying performance and memory capacity. We take advantage of high-performance features of CUDA for peer-to-peer GPU memory transfers and evaluate the performance of our algorithms on state-of-the-art GPU devices. We present parallel e ciency and performance results for simulations using multiple GPUs as system size, particle counts, and number of reactions grow. We also demonstrate multi-GPU performance in simulations of the Min protein system in E. coli. Moreover, our multi-GPU decomposition and load balancing approach can be generalized to other lattice-based problems.

  11. Exposure to Environmentally Relevant Concentrations of Genistein during Activation Does Not Affect Sperm Motility in the Fighting Fish Betta splendens

    Ethan D. Clotfelter


    Full Text Available Sperm collected from male fighting fish Betta splendens were activated in control water, water containing the ion-channel blocker gadolinium (a putative positive control, or water containing the isoflavone phytoestrogen genistein to determine the effects of acute genistein exposure on male reproductive function. Computer-assisted sperm analysis was used to quantify the proportion of sperm that were motile and the swimming velocity of those sperm. The highest concentration of gadolinium (100 μM tested was effective at reducing sperm motility and velocity, but neither concentration of genistein tested (3.7 nM or 3.7 μM significantly affected these sperm parameters. Our findings suggest that acute exposure to waterborne phytoestrogens during activation does not reduce the motility of fish sperm.

  12. Exposure to environmentally relevant concentrations of genistein during activation does not affect sperm motility in the fighting fish Betta splendens.

    Clotfelter, Ethan D; Gendelman, Hannah K


    Sperm collected from male fighting fish Betta splendens were activated in control water, water containing the ion-channel blocker gadolinium (a putative positive control), or water containing the isoflavone phytoestrogen genistein to determine the effects of acute genistein exposure on male reproductive function. Computer-assisted sperm analysis was used to quantify the proportion of sperm that were motile and the swimming velocity of those sperm. The highest concentration of gadolinium (100 μ M) tested was effective at reducing sperm motility and velocity, but neither concentration of genistein tested (3.7 nM or 3.7 μ M) significantly affected these sperm parameters. Our findings suggest that acute exposure to waterborne phytoestrogens during activation does not reduce the motility of fish sperm.

  13. Exposure to Environmentally Relevant Concentrations of Genistein during Activation Does Not Affect Sperm Motility in the Fighting Fish Betta splendens

    Clotfelter, Ethan D.; Hannah K Gendelman


    Sperm collected from male fighting fish Betta splendens were activated in control water, water containing the ion-channel blocker gadolinium (a putative positive control), or water containing the isoflavone phytoestrogen genistein to determine the effects of acute genistein exposure on male reproductive function. Computer-assisted sperm analysis was used to quantify the proportion of sperm that were motile and the swimming velocity of those sperm. The highest concentration of gadolinium (100 ...

  14. Preparation of Concentrated Chitosan/DNA Nanoparticle Formulations by Lyophilization for Gene Delivery at Clinically Relevant Dosages.

    Veilleux, Daniel; Nelea, Monica; Biniecki, Kristof; Lavertu, Marc; Buschmann, Michael D


    Chitosan/DNA polyplexes have been optimized for efficient and safe in vitro and in vivo gene delivery. Clinical application of this technology requires the development of formulations with higher concentrations to reach therapeutic dosages. Polyplexes were prepared using chitosan and EGFPLuc plasmids. Freeze-thawing and freeze-drying studies were performed to identify and optimize lyoprotectant and buffer contents in formulations. Freeze-dried samples were rehydrated in reduced volumes to increase their final DNA dose. Nanoparticle physicochemical properties were analyzed, and their transfection efficiency and cytotoxicity were measured in human embryonic kidney 293 cells. Data showed that 3.5 mM histidine buffer (pH 6.5) combined with one of 0.5% wt/vol sucrose, dextran 5 kDa, or trehalose was required to prevent polyplex aggregation during freeze-drying. Optimal formulations could be concentrated 20-fold, to a clinically desired ∼1 mg of DNA/mL, while maintaining near physiological pH and tonicity. Polyplexes were predominantly spherical, with diameters below 200 nm, polydispersity indexes below 0.32, and zeta potentials above +19 mV. Rehydrated formulations had transfection efficiencies no less than 65% of fresh polyplexes without excipients and had no effect on viability and metabolic activity of human embryonic kidney 293 cells. These concentrated formulations represent an important step toward clinical use of chitosan-based gene delivery systems.

  15. Experimentally constrained (p ,γ )89Y and (n ,γ )89Y reaction rates relevant to p -process nucleosynthesis

    Larsen, A. C.; Guttormsen, M.; Schwengner, R.; Bleuel, D. L.; Goriely, S.; Harissopulos, S.; Bello Garrote, F. L.; Byun, Y.; Eriksen, T. K.; Giacoppo, F.; Görgen, A.; Hagen, T. W.; Klintefjord, M.; Renstrøm, T.; Rose, S. J.; Sahin, E.; Siem, S.; Tornyi, T. G.; Tveten, G. M.; Voinov, A. V.; Wiedeking, M.


    The nuclear level density and the γ -ray strength function have been extracted for 89Y by using the Oslo method on 89Y(p ,p'γ )89Y coincidence data. The γ -ray strength function displays a low-energy enhancement consistent with previous observations in this mass region (Mo-9893). Shell-model calculations support the conclusion that the observed enhancement is due to strong, low-energy M 1 transitions at high excitation energies. The data were further used as input for calculations of the 88Sr(p ,γ )89Y and 88Y(n ,γ )89Y cross sections with the talys reaction code. Comparison with cross-section data, where available, as well as with values from the BRUSLIB library, shows a satisfying agreement.

  16. Influence of structure on reaction efficiency in surface catalysis. 1. Sensitivity to multiplet concentration and configuration

    Politowicz, P.A.; Kozak, J.J.


    A theoretical study of the role of configurational/geometrical factors in influencing the efficiency of diffusion-controlled reactions on surfaces has been initiated. The specific problem dealt with in this paper is to assess how different configurations of reaction centers can, by virtue of their disposition in reaction space, influence the efficiency of the process. The mean number (n) of steps taken by a diffusion coreactant before an irreversible reaction takes place at one of the catalytically active sites defining a multiplet has been calculated. This number (n) is related to the lifetime of the species and thence to the turnover number determined experimentally. Calculations are based on a lattice theory of diffusion-controlled processes proposed recently by the authors in which the theory of finite Markov processes is coupled with group theoretical arguments to yield a method for calculating exactly the mean, variance, skewness, and kurtosis of the underlying probability distribution function defining the process. Once the numerical results for (n) for different multiplet configurations have been presented, trends in the data are identified, and it is indicated how these can be understood in terms of the interplay of two factors: (1) the number and cluster configuration of the reaction centers and (2) a (discretized) correlation length k which specifies the distribution of singlets/ multiplets relative to a conveniently chosen reference point of the reaction space. In order to provide a concrete illustration of the manner in which these results may be used to interpret experiments, the presentation here focused on the work of Sinfelt and co-workers on the catalytic properties of bimetallic systems (and, in particular, on their studies of the hydrogenolysis of ethane and dehydrogenation of cyclohexane on Ni/Cu alloys.)

  17. May salivary gland secretory proteins from hematophagous leeches (Hirudo verbana reach pharmacologically relevant concentrations in the vertebrate host?

    Sarah Lemke

    Full Text Available Saliva of hematophagous leeches (Hirudo sp. contains bioactive proteins which allow the leech proper feeding and storage of ingested blood, but may also exert effects in the host. Leech therapy is used to treat many different ailments in humans, although only a small fraction of salivary proteins are characterized yet. Moreover, we do not know whether complete transfer of salivary proteins stored in the unicellular salivary glands in a leech to the host during feeding may generate concentrations that are sufficiently high to affect physiological processes in the host. Our 3D reconstruction of a portion of internal leech tissue from histological sections revealed that one leech contains approx. 37,000 salivary gland cells. Using tissue slices from pig liver and mouse skeletal muscle for reference, we obtained data for protein densities in leech salivary gland cells. As individual salivary cells are voluminous (67,000 µm(3 and the stored proteins are densely packed (approx. 500 µg/mm(3, we extrapolated that a single leech may contain up to 1.2 mg of salivary proteins. Analyzing protein extracts of unfed or fed leeches by 2D electrophoresis, we calculated the relative molar amounts of individual salivary proteins in the mass range of 17-60 kDa which may be released from a single leech during feeding. Distribution of these salivary proteins in the host (assumed plasma volume of 5 l may result in concentrations of individual compounds between 3 and 236 pmol/l. Such concentrations seem sufficiently high to exert biochemical interactions with target molecules in the host.

  18. Health and Climate-Relevant Pollutant Concentrations from a Carbon-Finance Approved Cookstove Intervention in Rural India.

    Aung, Ther W; Jain, Grishma; Sethuraman, Karthik; Baumgartner, Jill; Reynolds, Conor; Grieshop, Andrew P; Marshall, Julian D; Brauer, Michael


    Efforts to introduce more efficient stoves increasingly leverage carbon-finance to scale up dissemination of interventions. We conducted a randomized intervention study to evaluate a Clean Development Mechanism approved stove replacement impact on fuelwood usage, and climate and health-relevant air pollutants. We randomly assigned 187 households to either receive the intervention or to continue using traditional stoves. Measurements of fine particulate matter (PM2.5) and absorbance were conducted in cooking areas, village center and at upwind background site. There were minor and overlapping seasonal differences (post- minus preintervention change) between control and intervention groups for median (95% CI) fuel use (-0.60 (-1.02, -0.22) vs -0.52 (-1.07, 0.00) kg day(-1)), and 24 h absorbance (35 (18, 60) vs 36 (22, 50) × 10(-6) m(-1)); for 24 h PM2.5, there was a higher (139 (61,229) vs 73(-6, 156) μg m(-3))) increase in control compared to intervention homes between the two seasons. Forty percent of the intervention homes continued using traditional stoves. For intervention homes, absorbance-to-mass ratios suggest a higher proportion of black carbon in PM2.5 emitted from intervention compared with traditional stoves. Absent of field-based evaluation, stove interventions may be pursued that fail to realize expected carbon reductions or anticipated health and climate cobenefits.

  19. Optimisation of enzyme concentrations for unbranched reaction chains: the concept of combined response coefficient.

    de Vienne, D; Bost, B; Fiévet, J; Dillmann, C


    In the metabolic control theory, the control coefficient is a key parameter in quantifying the sensitivity of the flux towards an infinitesimal variation of enzyme activity. This concept does not apply just as it is for variations of enzyme concentrations whenever there is spatial, energy or resources limitations in the cell. Due to constraint on total enzyme concentration, the variation of concentration of any given enzyme may affect the concentrations of other enzymes. To take into account these correlations between enzyme concentrations, we propose the concept of "combined response coefficient". Its definition is similar to that of the control coefficient, but its mathematical expression is different. Its range of variation is from -infinity to +1, the null value corresponding to optimum enzyme concentration, i.e. to concentrations that maximise the flux, and the negative values to concentrations beyond the optimum value. A summation property could be derived using a simple weighting of the combined response coefficients, the sum of the weighed coefficient being 0.

  20. Speciation, Dissolution, and Redox Reactions of Chromium Relevant to Pretreatment and Separation of High-Level Tank Wastes

    Clark Sue B.; Dhanpat Rai; Linfeng Rao


    Chromium, one of the problematic elements in tank sludges, is considered the most important constituent in defining the total volume of high-level radioactive waste (HLW) glass. Current sludge washing processes (e.g. caustic leaching, 3 M NaOH) are not effective in removing Cr. This inefficient removal would result in production of an unacceptably large volume of HLW glass and thus a tremendous increase in the cost of waste disposal. This proposed research seeks to develop fundamental data for chromium (Cr) reactions that are not currently available but are essential for developing effective methodologies for removing Cr form high-level waste (HLW). Our objectives are to study (1) the dissolution of several solid phases (e.g., CrOOH, Cr2O3(c), Cr(OH)3, and Fe and Cr, binary hydroxides, identified to be important from sludge leaching studies) in highly alkaline solutions and in the presence of other electrolytes (e.g., carbonate, phosphate, sulfate, nitrite), and (2) the effect of the nature of Cr solid phases and aqueous species on their redox reactivity with a variety of potential oxidants (e.g., H2o2, persulfate, O2, and ferrate). This information will provide critical support for developing enhanced pretreatment strategies for removing Cr from HLW and will achieve a major cost reduction HLW disposal.

  1. Speciation, Dissolution, and Redox Reactions of Chromium Relevant to Pretreatment and Separation of High-Level Tank Wastes

    Dhapat Rai; Linfeng Rao


    Chromium, one of the problematic elements in tank sludges, is considered the most important constituent in defining the total volume of high-level radioactive waste (HLW) glass. Current sludge-washing processes (e.g. caustic leaching, 3 M NaOH) are not effective in removing Cr. Such inefficient removal would result in the production of an unacceptably large volume of HLW glass and thus a tremendous increase in the cost of waste disposal. This proposed research seeks to develop fundamental data for chromium (Cr) reactions that are not currently available but are essential for developing effective methodologies for removing Cr form high-level waste (HLW). Our objectives are to study (1) the dissolution of several solid phases (e.g., CrOOH, Cr2O3(c), Cr(OH)3, and Fe and Cr, binary hydroxides, identified to be important from sludge leaching studies) in highly alkaline solutions and in the presence of other electrolytes (e.g., carbonate, phosphate, sulfate, nitrite), and (2) the effect of the nature of Cr solid phases and aqueous species on their redox reactivity with a variety of potential oxidants (H2O2, persulfate, hypochlorite, etc.). This information will provide critical support for developing enhanced pretreatment strategies for removing Cr from HLW and will achieve a major cost reduction in HLW disposal.

  2. In utero exposure to environmentally relevant concentrations of PCB 153 and PCB 118 disrupts fetal testis development in sheep.

    Krogenæs, Anette K; Ropstad, Erik; Gutleb, Arno C; Hårdnes, Nina; Berg, Vidar; Dahl, Ellen; Fowler, Paul A


    Polychlorinated biphenyls (PCB) are environmental pollutants linked to adverse health effects including endocrine disruption and disturbance of reproductive development. This study aimed to determine whether exposure of pregnant sheep to three different mixtures of PCB 153 and PCB 118 affected fetal testis development. Ewes were treated by oral gavage from mating until euthanasia (d 134), producing three groups of fetuses with distinct adipose tissue PCB levels: high PCB 153/low PCB 118 (n = 13), high PCB 118/low PCB 153 (n = 14), and low PCB 153/low PCB 118 (n = 14). Fetal testes and blood samples were collected for investigation of testosterone, testis morphology, and testis proteome. The body weight of the offspring was lower in the high PCB compared to the low PCB group, but there were no significant differences in testis weight between groups when corrected for body weight. PCB exposure did not markedly affect circulating testosterone. There were no significant differences between groups in number of seminiferous tubules, Sertoli cell only tubules, and ratio between relative areas of seminiferous tubules and interstitium. Two-dimensional (2D) gel-based proteomics was used to screen for proteomic alterations in the high exposed groups relative to low PCB 153/low PCB 118 group. Twenty-six significantly altered spots were identified by liquid chromatography (LC)-mass spectroscopy (MS)/MS. Changes in protein regulation affected cellular processes as stress response, protein synthesis, and cytoskeleton regulation. The study demonstrates that in utero exposure to different environmental relevant PCB mixtures exerted subtle effects on developing fetal testis proteome but did not significantly disturb testis morphology and testosterone production.

  3. Buccal mucosal delivery of a potent peptide leads to therapeutically-relevant plasma concentrations for the treatment of autoimmune diseases.

    Jin, Liang; Boyd, Ben J; White, Paul J; Pennington, Michael W; Norton, Raymond S; Nicolazzo, Joseph A


    Stichodactyla helianthus neurotoxin (ShK) is an immunomodulatory peptide currently under development for the treatment of autoimmune diseases, including multiple sclerosis and rheumatoid arthritis by parenteral administration. To overcome the low patient compliance of conventional self-injections, we have investigated the potential of the buccal mucosa as an alternative delivery route for ShK both in vitro and in vivo. After application of fluorescent 5-Fam-ShK to untreated porcine buccal mucosa, there was no detectable peptide in the receptor chamber using an in vitro Ussing chamber model. However, the addition of the surfactants sodium taurodeoxycholate hydrate or cetrimide, and formulation of ShK in a chitosan mucoadhesive gel, led to 0.05-0.13% and 1.1% of the applied dose, respectively, appearing in the receptor chamber over 5h. Moreover, confocal microscopic studies demonstrated significantly enhanced buccal mucosal retention of the peptide (measured by mucosal fluorescence associated with 5-Fam-ShK) when enhancement strategies were employed. Administration of 5-Fam-ShK to mice (10mg/kg in a mucoadhesive chitosan-based gel (3%, w/v) with or without cetrimide (5%, w/w)) resulted in average plasma concentrations of 2.6-16.2nM between 2 and 6h, which were substantially higher than the pM concentrations required for therapeutic activity. This study demonstrated that the buccal mucosa is a promising administration route for the systemic delivery of ShK for the treatment of autoimmune diseases.

  4. The Effects of Differing Oxygen Concentrations on Reaction Time Performance at Altitude


    needed, and completing and reviewing the collection of information. Send comments regarding this burden estimate or any other aspect of this collection...Lumb, A. B. (2007). Just a little oxygen to breathe as you go off to sleep… is it always a good idea? British Journal of Anesthesia , 99 (6), 769-771...R. (1993). Methods for dealing with reaction time outliers. Psychological Bulletin, 114 (3), 510-532. Van Diest, I., Stegen, K., Van de Woestijne

  5. Effect of environmentally-relevant concentrations of nonylphenol on sexual differentiation in zebrafish: a multi-generational study

    Sun, Dong; Chen, Qi; He, Ning; Diao, Pan-pan; Jia, Li-xing; Duan, Shun-shan


    Nonylphenol (NP) is a persistent environmental chemical that can disrupt the organism’s endocrine system, and is detected in the surface water and sea. In this study, we investigated whether NP can alter transcriptional expression of sexual differentiation-related genes. Three generations of zebrafish were exposed to 0, 2, 20 and 200 μg·L−1 of NP, and transcriptional expression of sexual differentiation genes were assessed in 10, 20 and 40 dpf in the F1 and F2 generations. Growth of zebrafish exposed to 200 μg·L−1 of NP was inhibited at 125 dpf in the F1 generation. 20 μg·L−1 of NP resulted in 80% females in the F1 generation, but had no effect on the F2 generation. In terms of the sexual differentiation genes, the transcriptional expression of cyp19a1a and esr1 genes were upregulated in 20 μg·L−1 of NP in the F1 generation. But expression of the sexual differentiation genes were not affected in the F2 generation. Overall, NP could affect sexual differentiation and gene transcriptional expression in the F1 generation. The tolerance of contaminant in the offsprings was improved at low concentration. PMID:28230098

  6. Decomposition Reaction of Mixed Rare Earth Concentrate and Roasted with CaO and NaCl

    Wu Wenyuan; Hu Guangyong; Sun Shuchen; Chen Xudong; Tu Ganfeng


    The reaction of the mixed rare earth concentrate including monazite ( REPO4 ) and bastnaesite ( REFCO3 )decomposed by CaO and NaCl additives at the temperature range from 100 to 1000 ℃ was studied by means of XRD and TG-DTA.The results show that when CaO and NaCl are not added, only REFCO3 can be decomposed at the temperature of 377 ~ 450 ℃.The decomposition products include REOF, RE2O3 and CeO2.However, REFCO3 can not be decomposed.When CaO is added, the decomposition reactions occur at the temperature range from 660 to 750 ℃.CaO has three decomposition functions: ( 1 ) REPO4 can be decomposed by CaO and the decomposition products include RE2O3 and Ca3 (PO4)2; (2) CaO can decompose REOF, and the decomposition products are RE2O3 and CaF2; (3)CaO can decompose REPO4 with CaF2, and the decomposition products are RE2 O3, Ca5 F( PO4 )3.The decomposition ratio of the mixed rare earth concentrate increased obviously, when CaO and NaC1 were added.NaC1 can supply the liquid for the reaction, improve the mass transfer process and accelerate the reaction.At the same time, NaC1 participated in the reaction that REPO4 was decomposed by CaO.

  7. Toxicity of TiO2 nanoparticles on soil nitrification at environmentally relevant concentrations: Lack of classical dose-response relationships.

    Simonin, Marie; Martins, Jean M F; Le Roux, Xavier; Uzu, Gaëlle; Calas, Aude; Richaume, Agnès


    Titanium-dioxide nanoparticles (TiO2-NPs) are increasingly released in agricultural soils through, e.g. biosolids, irrigation or nanoagrochemicals. Soils are submitted to a wide range of concentrations of TiO2-NPs depending on the type of exposure. However, most studies have assessed the effects of unrealistically high concentrations, and the dose-response relationships are not well characterized for soil microbial communities. Here, using soil microcosms, we assessed the impact of TiO2-NPs at concentrations ranging from 0.05 to 500 mg kg(-1 )dry-soil, on the activity and abundance of ammonia-oxidizing archaea (AOA) and bacteria (AOB), and nitrite-oxidizing bacteria (Nitrobacter and Nitrospira). In addition, aggregation and oxidative potential of TiO2-NPs were measured in the spiking suspensions, as they can be important drivers of TiO2-NPs toxicity. After 90 days of exposure, non-classical dose-response relationships were observed for nitrifier abundance or activity, making threshold concentrations impossible to compute. Indeed, AOA abundance was reduced by 40% by TiO2-NPs whatever the concentration, while Nitrospira was never affected. Moreover, AOB and Nitrobacter abundances were decreased mainly at intermediate concentrations nitrification was reduced by 25% at the lowest (0.05 mg kg(-1)) and the highest (100 and 500 mg kg(-1)) TiO2-NPs concentrations. Path analyses indicated that TiO2-NPs affected nitrification through an effect on the specific activity of nitrifiers, in addition to indirect effects on nitrifier abundances. Altogether these results point out the need to include very low concentrations of NPs in soil toxicological studies, and the lack of relevance of classical dose-response tests and ecotoxicological dose metrics (EC50, IC50…) for TiO2-NPs impact on soil microorganisms.

  8. Excited state intramolecular charge transfer reaction in non-aqueous reverse micelles: Effects of solvent confinement and electrolyte concentration

    Tuhin Pradhan; Harun Al Rasid Gazi; Biswajit Guchhait; Ranjit Biswas


    Steady state and time resolved fluorescence emission spectroscopy have been employed to investigate the effects of solvent confinement and electrolyte concentration on excited state intramolecular charge transfer (ICT) reaction in 4-(1-pyrrolidinyl) benzonitrile (P5C), 4-(1-piperidinyl) benzonitrile (P6C), and 4-(1-morpholenyl) benzonitrile (M6C) in AOT/n-heptane/acetonitrile and AOT/n-heptane/methanol reverse micelles. Dramatic confinement effects have been revealed via a huge reduction (factor ranging between 100 and 20) over bulk values of both equilibrium and reaction rate constants. A strong dependence on the size of the confinement () of these quantities has also been observed. dependent average static dielectric constant, viscosity and solvation time-scale have been determined. Estimated dielectric constants for confined methanol and acetonitrile show a decrease from the respective bulk values by a factor of 3-5 and viscosities increased by a factor of 2 at the highest considered. Addition of electrolyte at = 5 for acetonitrile is found to produce a linear increase of confined solvent viscosity but leads to a non-monotonic electrolyte concentration dependence of average solvation time. Reaction rate constant is found to decrease linearly with electrolyte concentration for P5C and P6C but non-monotonically for M6C, the highest decrease for all the molecules being ∼ 20% over the value in the absence of added electrolyte in the solvent pool. The observed huge reduction in reaction rate constant is attributed to the effects of decreased solution polarity, enhanced viscosity and slowed-down solvent reorganization of the solvent under confinement in these non-aqueous reverse micelles.

  9. Even low alcohol concentrations affect obstacle avoidance reactions in healthy senior individuals.

    Hegeman, J.; Weerdesteijn, V.G.M.; Bemt, B.J.F. van den; Nienhuis, B.; Limbeek, J. van; Duysens, J.E.J.


    BACKGROUND: Alcohol is a commonly used social drug and driving under influence is a well-established risk factor for traffic accidents1. To improve road safety, legal limits are set for blood alcohol concentration (BAC) and driving, usually at 0.05% (most European countries) or 0.08% (most US states

  10. Kinetics of heterogeneous reaction of ozone with linoleic acid and its dependence on temperature, physical state, RH, and ozone concentration.

    Zeng, Guang; Holladay, Sara; Langlois, Danielle; Zhang, Yunhong; Liu, Yong


    Heterogeneous reaction between ozone and linoleic acid (LA) thin film was investigated by a flow reactor coupled to attenuated total reflection infrared spectroscopy (FR-ATR-IR) over wide ranges of temperature, relative humidity (RH), and ozone concentration under atmospheric pressure condition. Pseudo-first-order rate constants kapp and overall reactive uptake coefficients γ were acquired on the basis of changes in absorbance from peaks located near 1743, 1710, 1172, and 1110 cm(-1), which can be assigned to C═O in ester, C═O in acid, and C-C and C-O stretching modes, respectively. Results showed that the kapp and γ increased nearly by a factor of 6 with increasing temperatures from 258 to 314 K. It was noted the temperature effect on the reaction kinetics was much more pronounced at lower temperatures. Such behavior can be explained by a change in the physical state of LA at lower temperatures. In addition, kapp and γ were enhanced by 2-fold as the RH increased from 0 to 80%. Moreover, the effect of ozone concentration on the reaction kinetics was reported for the first time. kapp was found to display a Langmuir-Hinshelwood dependence on ozone concentration with KO3 = (1.146 ± 0.017) × 10(-15) molecules cm(-3) and k[S] = 0.0522 ± 0.0004 s(-1), where KO3 is a parameter that describes the partitioning of ozone to the thin film surface, and k[S] is the maximum pseudo-first-order coefficient at high ozone concentration. Furthermore, yields and hygroscopic properties of reaction products were also investigated by FTIR spectroscopy. The intensity ratio of two C═O stretching bands, A1743/A1710, which was utilized as an indicator of the product yields, increased sharply with increasing temperatures in the lower temperature region (258-284 K), and then remained nearly constant in the higher temperature region (284-314 K). The product yields showed no significant variation with RH, for the intensity ratio of A1743/A1710 barely changed in the wide RH range 0

  11. Impact of TiO₂ and ZnO nanoparticles at predicted environmentally relevant concentrations on ammonia-oxidizing bacteria cultures under ammonia oxidation.

    Luo, Zhuanxi; Qiu, Zhaozheng; Chen, Zheng; Du Laing, Gijs; Liu, Aifen; Yan, Changzhou


    Increased application of titanium dioxide and zinc oxide nanoparticles (nano-TiO2 and nano-ZnO) raises concerns related to their environmental impacts. The effects that such nanoparticles have on environmental processes and the bacteria that carry them out are largely unknown. In this study, ammonia-oxidizing bacteria (AOB) enrichment cultures, grown from surface sediments taken from an estuary wetland in Fujian Province, China, were spiked with nano-TiO2 and nano-ZnO (with an average size of 32 and 43 nm, respectively) at predicted environmentally relevant concentrations (≤2 mg L(-1)) to determine their impacts on ammonia oxidation and the mechanisms involved. Results showed that higher nano-TiO2 concentrations significantly inhibited ammonia oxidation in enrichment cultures. It is noteworthy that the average ammonia oxidation rate was significantly correlated to the Shannon index, the Simpson's index, and AOB abundance. This suggested that ammonia oxidation inhibition primarily resulted from a reduction of AOB biodiversity and abundance. However, AOB biodiversity and abundance as well as the average ammonia oxidation rate were not inhibited by nano-ZnO at predicted environmentally relevant concentrations. Accordingly, an insignificant correlation was established between biodiversity and abundance of the AOB amoA gene and the average ammonia oxidation rate under nano-ZnO treatments. AOB present in samples belonged to the β-Proteobacteria class with an affinity close to Nitrosospira and Nitrosomonas genera. This suggested that identified impacts of nano-TiO2 and nano-ZnO on ammonia oxidation processes can be extrapolated to some extent to natural aquatic environments. Complex impacts on AOB may result from different nanomaterials present in aquatic environments at various ambient conditions. Further investigation on how and to what extent different nanomaterials influence AOB diversity and abundance and their subsequent ammonia oxidation processes is therefore

  12. Transient reaction of an elastic half-plane on a source of a concentrated boundary disturbance

    Okonechnikov, A. S.; Tarlakovski, D. V.; Ul'yashina, A. N.; Fedotenkov, G. V.


    One of the key problems in studying the non-stationary processes of solid mechanics is obtaining of influence functions. These functions serve as solutions for the problems of effect of sudden concentrated loads on a body with linear elastic properties. Knowledge of the influence functions allows us to obtain the solutions for the problems with non-mixed boundary and initial conditions in the form of quadrature formulae with the help of superposition principle, as well as get the integral governing equations for the problems with mixed boundary and initial conditions. This paper offers explicit derivations for all nonstationary surface influence functions of an elastic half-plane in a plane strain condition. It is achieved with the help of combined inverse transform of a Fourier-Laplace integral transformation. The external disturbance is both dynamic and kinematic. The derived functions in xτ-domain are studied to find and describe singularities and are supplemented with graphs.

  13. Inhibition of peroxynitrite-mediated DNA strand cleavage and hydroxyl radical formation by aspirin at pharmacologically relevant concentrations: Implications for cancer intervention

    Chen, Wei [Division of Biomedical Sciences, Edward Via Virginia College of Osteopathic Medicine, Virginia Tech Corporate Research Center, Blacksburg, VA 24060 (United States); College of Food Science and Biotechnology, Zhejiang Gongshang University, Hangzhou 310035 (China); Department of Food Science and Technology, Virginia Polytechnic Institute and State University, Blacksburg, VA 24061 (United States); Zhu, Hong; Jia, Zhenquan [Division of Biomedical Sciences, Edward Via Virginia College of Osteopathic Medicine, Virginia Tech Corporate Research Center, Blacksburg, VA 24060 (United States); Li, Jianrong [College of Food Science and Biotechnology, Zhejiang Gongshang University, Hangzhou 310035 (China); Misra, Hara P. [Division of Biomedical Sciences, Edward Via Virginia College of Osteopathic Medicine, Virginia Tech Corporate Research Center, Blacksburg, VA 24060 (United States); Zhou, Kequan, E-mail: [Department of Nutrition and Food Science, Wayne State University, Detroit, MI 48202 (United States); Li, Yunbo, E-mail: [Division of Biomedical Sciences, Edward Via Virginia College of Osteopathic Medicine, Virginia Tech Corporate Research Center, Blacksburg, VA 24060 (United States)


    Epidemiological studies have suggested that the long-term use of aspirin is associated with a decreased incidence of human malignancies, especially colorectal cancer. Since accumulating evidence indicates that peroxynitrite is critically involved in multistage carcinogenesis, this study was undertaken to investigate the ability of aspirin to inhibit peroxynitrite-mediated DNA damage. Peroxynitrite and its generator 3-morpholinosydnonimine (SIN-1) were used to cause DNA strand breaks in {phi}X-174 plasmid DNA. We demonstrated that the presence of aspirin at concentrations (0.25-2 mM) compatible with amounts in plasma during chronic anti-inflammatory therapy resulted in a significant inhibition of DNA cleavage induced by both peroxynitrite and SIN-1. Moreover, the consumption of oxygen caused by 250 {mu}M SIN-1 was found to be decreased in the presence of aspirin, indicating that aspirin might affect the auto-oxidation of SIN-1. Furthermore, EPR spectroscopy using 5,5-dimethylpyrroline-N-oxide (DMPO) as a spin trap demonstrated the formation of DMPO-hydroxyl radical adduct (DMPO-OH) from authentic peroxynitrite, and that aspirin at 0.25-2 mM potently diminished the radical adduct formation in a concentration-dependent manner. Taken together, these results demonstrate for the first time that aspirin at pharmacologically relevant concentrations can inhibit peroxynitrite-mediated DNA strand breakage and hydroxyl radical formation. These results may have implications for cancer intervention by aspirin.

  14. The Non-Linear Child: Ontogeny, Isoniazid Concentration, and NAT2 Genotype Modulate Enzyme Reaction Kinetics and Metabolism

    Zoe Rogers


    Full Text Available N-acetyltransferase 2 (NAT2 catalyzes the acetylation of isoniazid to N-acetylisoniazid. NAT2 polymorphism explains 88% of isoniazid clearance variability in adults. We examined the effects of clinical and genetic factors on Michaelis-Menten reaction kinetic constants of maximum velocity (Vmax and affinity (Km in children 0–10 years old. We measured the rates of isoniazid elimination and N-acetylisoniazid production in the blood of 30 children. Since maturation effects could be non-linear, we utilized a pharmacometric approach and the artificial intelligence method, multivariate adaptive regression splines (MARS, to identify factors predicting NAT2 Vmax and Km by examining clinical, genetic, and laboratory factors in toto. Isoniazid concentration predicted both Vmax and Km and superseded the contribution of NAT2 genotype. Age non-linearly modified the NAT2 genotype contribution until maturation at ≥5.3 years. Thus, enzyme efficiency was constrained by substrate concentration, genes, and age. Since MARS output is in the form of basis functions and equations, it allows multiscale systems modeling from the level of cellular chemical reactions to whole body physiological parameters, by automatic selection of significant predictors by the algorithm.

  15. Dependence of reaction rate of pyrite oxidation on temperature, pH and oxidant concentration

    LU; Long; WANG; Rucheng; XUE; Jiyue; CHEN; Fanrong; CHEN; J


    The kinetic sstudy of pyrite oxidation was performed in a series of experiments by a mixed flow reactor. The release rates of Fe(II) are in the order of 3.22×10-9-5.51×10-7 mol·m-2·s-1 at temperature (T ) 25 to 44℃, initial pH (pH )1.4 to 2.7, and initial Fe(III) concentration ([Fe(III)]I) 10-5 to 5×10-3 mol·kg-1. The release rate of Fe(II) increased with increasing T or/and pH or/and [Fe(III)]I in the above range. The rate law and activation energy of pyrite oxidation were derived by statistical analyses of Rfe(II) vs. [Fe(III)]I, Rfe(II) vs. pH and Rfe(II) vs. T, and are given as (1) Rate law: Rfe(II)=104.65e-64.54×103/8.31T[Fe(III)]i0.6./[H+]0.45 ; (2) activation energy: 64.54 ( 8.07 kJ·mol-1. The expression can be applied to more cases (e.g., quantifying the pollutant released from sulfide-rich mining waste and assessing reliable performance of underground repository sites where pyrite acts as an engineered barrier material). Using the rate law derived from this study, the magnitude of the pollutants transferred to secondary phases, soil and water from oxidized pyrite during Jiguanshan mine waste weathering was preliminarily estimated. The estimated magnitude is very high, suggesting that the pile has possibly posed significant impact on the water quality in this region.

  16. In vitro assays in natural products research - a matter of concentration and relevance to in vivo administration using resveratrol, α-mangostin/γ-mangostin and xanthohumol as examples.

    Willson, C M; Grundmann, O


    Herbal or botanical dietary supplements are an ever increasingly popular category of products in the United States and around the world. In vitro data can provide meaningful insight into the potential target and mechanism of action for a proposed active compound but may also be misused to promote a supplement to consumers with unverified health claims. In vitro data need to be considered alongside pharmacokinetic and pharmacodynamic data in preclinical animal and clinical human trials. While considerable activity of compounds and extracts in vitro may lead to further testing in vivo, in many instances, concentrations tested in cell lines or isolated targets are not achievable at the target site in vivo. Thus, whether the in vitro data are relevant to humans after oral administration is questionable. This review will discuss this discrepancy using in vitro and in vivo data of resveratrol, xanthones (α-mangostin and γ-mangostin) and xanthohumol.

  17. Relevance analysis and short-term prediction of PM2.5 concentrations in Beijing based on multi-source data

    Ni, X. Y.; Huang, H.; Du, W. P.


    The PM2.5 problem is proving to be a major public crisis and is of great public-concern requiring an urgent response. Information about, and prediction of PM2.5 from the perspective of atmospheric dynamic theory is still limited due to the complexity of the formation and development of PM2.5. In this paper, we attempted to realize the relevance analysis and short-term prediction of PM2.5 concentrations in Beijing, China, using multi-source data mining. A correlation analysis model of PM2.5 to physical data (meteorological data, including regional average rainfall, daily mean temperature, average relative humidity, average wind speed, maximum wind speed, and other pollutant concentration data, including CO, NO2, SO2, PM10) and social media data (microblog data) was proposed, based on the Multivariate Statistical Analysis method. The study found that during these factors, the value of average wind speed, the concentrations of CO, NO2, PM10, and the daily number of microblog entries with key words 'Beijing; Air pollution' show high mathematical correlation with PM2.5 concentrations. The correlation analysis was further studied based on a big data's machine learning model- Back Propagation Neural Network (hereinafter referred to as BPNN) model. It was found that the BPNN method performs better in correlation mining. Finally, an Autoregressive Integrated Moving Average (hereinafter referred to as ARIMA) Time Series model was applied in this paper to explore the prediction of PM2.5 in the short-term time series. The predicted results were in good agreement with the observed data. This study is useful for helping realize real-time monitoring, analysis and pre-warning of PM2.5 and it also helps to broaden the application of big data and the multi-source data mining methods.

  18. Reduction of non-enzymatic browning of orange juice and semi-concentrates by removal of reaction substrate.

    Sharma, Satish K; Juyal, Shashibala; Rao, V K; Yadav, V K; Dixit, A K


    A study was conducted to standardize the technology for the removal of amino acids (one of the browning reaction substrates) from sweet orange cv. Malta Common juice to reduce colour and quality deterioration in single strength juice and during subsequent concentration. Juice of sweet orange (Citrus sinensis) cv. Malta Common fruits was extracted by screw type juice extractor, preserved in 500 ppm SO2 and clarified by using "Pectinase CCM" enzyme (0.2% for 2 h at 50 ± 2 °C). For removal of amino acids juice was passed under gravity through a glass column packed with an acidic cation exchange resin (CER), Dowex-50 W and quantity to be treated in one lot was standardized. The CER treated and untreated juices were concentrated to 15 and 30°Brix in a rotary vacuum evaporator. Results indicate that 121 ml of orange juice when passed through a glass column (5 cm internal diameter) packed with cation exchange resin (Dowex-50 W) upto a height of 8 cm, could remove about 98.4% of the amino acids with minimum losses in other juice constituents. With cation exchange resin treatment, the non-enzymatic browning and colour deterioration of orange juice semi-concentrates was reduced to about 3 folds in comparison to untreated counterparts. The retention of vitamin C and sugars was also better in semi-concentrates prepared from cation exchange resin treated juice. Thus, cation exchange resin treatment of orange juice prior to concentration and storage is highly beneficial in reduction of non-enzymatic browning, colour deterioration and retention of nutritional, sensory quality of product during preparation and storage.

  19. Final report on LDRD project: A phenomenological model for multicomponent transport with simultaneous electrochemical reactions in concentrated solutions



    A phenomenological model was developed for multicomponent transport of charged species with simultaneous electrochemical reactions in concentrated solutions, and was applied to model processes in a thermal battery cell. A new general framework was formulated and implemented in GOMA (a multidimensional, multiphysics, finite-element computer code developed and being enhanced at Sandia) for modeling multidimensional, multicomponent transport of neutral and charged species in concentrated solutions. The new framework utilizes the Stefan-Maxwell equations that describe multicomponent diffusion of interacting species using composition-insensitive binary diffusion coefficients. The new GOMA capability for modeling multicomponent transport of neutral species was verified and validated using the model problem of ternary gaseous diffusion in a Stefan tube. The new GOMA-based thermal battery computer model was verified using an idealized battery cell in which concentration gradients are absent; the full model was verified by comparing with that of Bernardi and Newman (1987) and validated using limited thermal battery discharge-performance data from the open literature (Dunning 1981) and from Sandia (Guidotti 1996). Moreover, a new Liquid Chemkin Software Package was developed, which allows the user to handle manly aspects of liquid-phase kinetics, thermodynamics, and transport (particularly in terms of computing properties). Lastly, a Lattice-Boltzmann-based capability was developed for modeling pore- or micro-scale phenomena involving convection, diffusion, and simplified chemistry; this capability was demonstrated by modeling phenomena in the cathode region of a thermal battery cell.

  20. Neutron capture reactions relevant to s-process and p-process in the domain of the $N=50$ shell closure

    Dutta, Saumi; Bhattacharyya, Abhijit


    Radiative thermal neutron capture cross sections for nuclei participating in s-process and p-process nucleosynthesis in and around $N=50$ closed neutron shell have been calculated in statistical semi-microscopic Hauser-Feshbach approach for the energy range of astrophysical interest. A folded optical model potential is constructed utilizing the standard DDM3Y real nucleon-nucleon interaction. The folding of the interaction with target radial matter densities, obtained from the relativistic-mean-field approach, is done in coordinate space using the spherical approximation. The standard nuclear reaction code TALYS1.8 is used for cross-section calculation. The cross sections are compared with experimental results and reasonable agreements are found for almost all cases. Maxwellian-averaged cross sections (MACS) for the nuclei are presented at a single thermal energy of 30 keV relevant to s-process. We have also presented the MACS values over a range of energy from 5 to 100 keV for neutron magic nuclei with $(N=5...

  1. Myosin proteins identified from masseter muscle using quantitative reverse transcriptase-polymerase chain reaction--a pilot study of the relevance to orthodontics.

    Suchak, Archna; Hunt, Nigel P; Shah, Rishma; Sinanan, Andrea C M; Lloyd, Tim; Lewis, Mark P


    There is a clearly established relationship between masticatory muscle structure and facial form. Human studies in this area, however, have been limited, especially in consideration of the myosin heavy chain (MyHC) family of contractile proteins. The aim of this pilot study was to assess if differences were detectable between genotype with respect to MyHC isoforms and the vertical facial phenotype in a sample of nine Caucasian female patients, age range 18-49 years, using a novel rapid technique. Masseter muscle biopsies were taken from patients with a range of vertical facial form. The levels of expression of the MyHC isoform genes MYH 1, 2, 3, 6, 7, and 8 were compared with the expression in a female calibrator patient aged 23 years with normal vertical facial form, using quantitative reverse transcriptase-polymerase chain reaction (RT-PCR) analysis. Statistical analysis was undertaken using Pearson correlation coefficient. The results showed that there were distinct differences in gene expression between patients with a wide range of variation although changes in MYH1 were consistent with one cephalometric variable, the maxillo-mandibular angle. The full procedure, from start to finish, can be completed within half a day. Rapid genotyping of patients in this way could reveal important information of relevance to treatment. This technology has potential as a diagnostic and prognostic aid when considering correction of certain malocclusions.

  2. Response of Lemna gibba L. to high and environmentally relevant concentrations of ibuprofen: Removal, metabolism and morpho-physiological traits for biomonitoring of emerging contaminants.

    Di Baccio, D; Pietrini, F; Bertolotto, P; Pérez, S; Barcelò, D; Zacchini, M; Donati, E


    The increasing worldwide consumption of pharmaceuticals and personal care products such as ibuprofen (IBU) is leading to the widespread and persistent occurrence of these chemicals and their transformation products in soils and waters. Although at low concentrations, the continuous discharge of these micropollutants and the incomplete removal by the actual wastewater treatments can provoke accumulation in the environment with risks for the trophic chain. Non-target organisms as duckweed can be used for the environmental monitoring of pharmaceutical emerging contaminants. In this work, plants of Lemna gibba L. were exposed to high (0.20 and 1mgL(-1)) and environmentally relevant (0.02mgL(-1)) concentrations of IBU to investigate their removal and metabolization capacity. The main oxidized IBU metabolites in humans (hydroxy-IBU and carboxy-IBU) were determined in the intact plants and in the growth solutions, together with non-destructive physiological parameters and phytotoxic indicators. The IBU uptake increased with the increasing of IBU concentration in the medium, but the relative accumulation of the pharmaceutical and generation of hydroxy-IBU was higher in presence of the lower IBU treatments. Carboxy-IBU was not found in the plant tissue and solutions. The changes observed in growth and photosynthetic performances were not able to induce phyto-toxic effects. Apart from a mean physical-chemical degradation of 8.2%, the IBU removal by plants was highly efficient (89-92.5%) in all the conditions tested, highlighting the role of L. gibba in the biodegradation of emerging contaminants.

  3. Beta-defensin-2 protein is a serum biomarker for disease activity in psoriasis and reaches biologically relevant concentrations in lesional skin.

    Patrick A M Jansen

    Full Text Available BACKGROUND: Previous studies have extensively documented antimicrobial and chemotactic activities of beta-defensins. Human beta-defensin-2 (hBD-2 is strongly expressed in lesional psoriatic epidermis, and recently we have shown that high beta-defensin genomic copy number is associated with psoriasis susceptibility. It is not known, however, if biologically and pathophysiologically relevant concentrations of hBD-2 protein are present in vivo, which could support an antimicrobial and proinflammatory role of beta-defensins in lesional psoriatic epidermis. METHODOLOGY/PRINCIPAL FINDINGS: We found that systemic levels of hBD-2 showed a weak but significant correlation with beta defensin copy number in healthy controls but not in psoriasis patients with active disease. In psoriasis patients but not in atopic dermatitis patients, we found high systemic hBD-2 levels that strongly correlated with disease activity as assessed by the PASI score. Our findings suggest that systemic levels in psoriasis are largely determined by secretion from involved skin and not by genomic copy number. Modelling of the in vivo epidermal hBD-2 concentration based on the secretion rate in a reconstructed skin model for psoriatic epidermis provides evidence that epidermal hBD-2 levels in vivo are probably well above the concentrations required for in vitro antimicrobial and chemokine-like effects. CONCLUSIONS/SIGNIFICANCE: Serum hBD-2 appears to be a useful surrogate marker for disease activity in psoriasis. The discrepancy between hBD-2 levels in psoriasis and atopic dermatitis could explain the well known differences in infection rate between these two diseases.

  4. The Sakaguchi reaction product quenches phycobilisome fluorescence, allowing determination of the arginine concentration in cells of Anabaena strain PCC 7120.

    Ke, Shan; Haselkorn, Robert


    The filamentous cyanobacterium Anabaena fixes nitrogen in specialized cells called heterocysts. The immediate product of fixation, ammonia, is known to be assimilated by addition to glutamate to make glutamine. How fixed nitrogen is transported along the filament to the 10 to 20 vegetative cells that separate heterocysts is unknown. N-fixing heterocysts accumulate an insoluble polymer containing aspartate and arginine at the cell poles. Lockau's group has proposed that the polymer is degraded at the poles to provide a mobile carrier, arginine, to the vegetative cells (R. Richter, M. Hejazi, R. Kraft, K. Ziegler, and W. Lockau, Eur. J. Biochem. 263:163-169, 1999). We wished to use the Sakaguchi reaction for arginine to determine the relative cellular concentration of arginine along the filament. At present, the methods for measuring absorption of the Sakaguchi reaction product at 520 nm are insufficiently sensitive for that purpose. However, that product quenches the fluorescence of phycobiliproteins, which we have adapted to a determination of arginine. Our results are consistent with the proposal that arginine is a principal nitrogen carrier from heterocysts to vegetative cells in Anabaena.

  5. Derivation of the reduced reaction mechanisms of ozone depletion events in the Arctic spring by using concentration sensitivity analysis and principal component analysis

    Cao, Le; Wang, Chenggang; Mao, Mao; Grosshans, Holger; Cao, Nianwen


    The ozone depletion events (ODEs) in the springtime Arctic have been investigated since the 1980s. It is found that the depletion of ozone is highly associated with an auto-catalytic reaction cycle, which involves mostly the bromine-containing compounds. Moreover, bromide stored in various substrates in the Arctic such as the underlying surface covered by ice and snow can be also activated by the absorbed HOBr. Subsequently, this leads to an explosive increase of the bromine amount in the troposphere, which is called the "bromine explosion mechanism". In the present study, a reaction scheme representing the chemistry of ozone depletion and halogen release is processed with two different mechanism reduction approaches, namely, the concentration sensitivity analysis and the principal component analysis. In the concentration sensitivity analysis, the interdependence of the mixing ratios of ozone and principal bromine species on the rate of each reaction in the ODE mechanism is identified. Furthermore, the most influential reactions in different time periods of ODEs are also revealed. By removing 11 reactions with the maximum absolute values of sensitivities lower than 10 %, a reduced reaction mechanism of ODEs is derived. The onsets of each time period of ODEs in simulations using the original reaction mechanism and the reduced reaction mechanism are identical while the maximum deviation of the mixing ratio of principal bromine species between different mechanisms is found to be less than 1 %. By performing the principal component analysis on an array of the sensitivity matrices, the dependence of a particular species concentration on a combination of the reaction rates in the mechanism is revealed. Redundant reactions are indicated by principal components corresponding to small eigenvalues and insignificant elements in principal components with large eigenvalues. Through this investigation, aside from the 11 reactions identified as unimportant in the concentration

  6. Biological assessments of a mixture of endocrine disruptors at environmentally relevant concentrations in water following UV/H{sub 2}O{sub 2} oxidation

    Chen, P.-J. [Department of Civil and Environmental Engineering, Duke University (United States); Integrated Toxicology Program, Nicolas School of Environment and Earth Science, Duke University (United States); Rosenfeldt, Erik J. [Department of Civil and Environmental Engineering, Duke University (United States); Kullman, Seth W. [Integrated Toxicology Program, Nicolas School of Environment and Earth Science, Duke University (United States); Hinton, David E. [Integrated Toxicology Program, Nicolas School of Environment and Earth Science, Duke University (United States); Linden, Karl G. [Department of Civil and Environmental Engineering, Duke University (United States)]. E-mail:


    Numerous studies have investigated degradation of individual endocrine disrupting compounds (EDCs) in lab or natural waters. However, natural variations in water matrices and mixtures of EDCs in the environment may confound analysis of the treatment efficiency. Because chemical based analytical methods cannot represent the combined or synergistic activities between water quality parameters and/or the EDC mixtures at environmentally relevant concentrations ({mu}g L{sup -1}-ng L{sup -1}), bioanalytical assessments of residual estrogenic activity in treated water were used to evaluate the performance of the UV based advanced oxidation process for estrogenic contaminants in water. Four EDCs including estradiol (E{sub 2}), ethinyl estradiol (EE{sub 2}), bisphenol-A (BPA) and nonylphenol (NP) were spiked individually or as a mixture at {mu}g L{sup -1}-ng L{sup -1} in laboratory or natural river water. The removal rates of estrogenic activity were quantitatively evaluated by in vitro yeast estrogen screen (YES) and in vivo Vitellogenin (VTG) assays with Japanese medaka fish (Oryzias latipes). UV in combination with 10 ppm H{sub 2}O{sub 2} as an oxidation process was capable of decreasing in vitro and in vivo estrogenic activity, however, in vivo estrogenic activity of the EDC mixture in natural water was not completely removed at UV fluence up to 2000 mJ cm{sup -2}. The removal rates of in vitro estrogenic activity of the EDC mixtures were lower than those observed for single compounds, and slower in natural waters, likely due to lower steady-state concentrations of hydroxyl radicals ({center_dot}OH) in the presence of {center_dot}OH scavengers from the water matrix and EDC mixture.

  7. Molecular and phenetic characterization of the bacterial assemblage of Hot Lake, WA, an environment with high concentrations of magnesium sulphate, and its relevance to Mars

    Kilmer, Brian R.; Eberl, Timothy C.; Cunderla, Brent; Chen, Fei; Clark, Benton C.; Schneegurt, Mark A.


    Hot Lake (Oroville, WA) is an athalassohaline epsomite lake that can have precipitating concentrations of MgSO4 salts, mainly epsomite. Little biotic study has been done on epsomite lakes and it was unclear whether microbes isolated from epsomite lakes and their margins would fall within recognized halotolerant genera, common soil genera or novel phyla. Our initial study cultivated and characterized epsotolerant bacteria from the lake and its margins. Approximately 100 aerobic heterotrophic microbial isolates were obtained by repetitive streak-plating in high-salt media including either 10% NaCl or 2 M MgSO4. The collected isolates were all bacteria, nearly evenly divided between Gram-positive and Gram-negative clades, the most abundant genera being Halomonas, Idiomarina, Marinobacter, Marinococcus, Nesterenkonia, Nocardiopsis and Planococcus. Bacillus, Corynebacterium, Exiguobacterium, Kocuria and Staphylococcus also were cultured. This initial study included culture-independent community analysis of direct DNA extracts of lake margin soil using PCR-based clone libraries and 16S rRNA gene phylogeny. Clones assigned to Gram-positive bacterial clades (70% of total clones) were dominated by sequences related to uncultured actinobacteria. There were abundant Deltaproteobacteria clones related to bacterial sulphur metabolisms and clones of Legionella and Coxiella. These epsomite lake microbial communities seem to be divided between bacteria primarily associated with hyperhaline environments rich in NaCl and salinotolerant relatives of common soil organisms. Archaea appear to be in low abundance and none were isolated, despite near-saturated salinities. Growth of microbes at very high concentrations of magnesium and other sulphates has relevance to planetary protection and life-detection missions to Mars, where scant liquid water may form as deliquescent brines and appear as eutectic liquids.

  8. Clinically relevant concentrations of fosfomycin combined with polymyxin B, tobramycin or ciprofloxacin enhance bacterial killing of Pseudomonas aeruginosa, but do not suppress the emergence of fosfomycin resistance.

    Walsh, Clare C; Landersdorfer, Cornelia B; McIntosh, Michelle P; Peleg, Anton Y; Hirsch, Elizabeth B; Kirkpatrick, Carl M; Bergen, Phillip J


    Fosfomycin resistance occurs rapidly with monotherapy. This study systematically investigated bacterial killing and emergence of fosfomycin resistance with fosfomycin combinations against Pseudomonas aeruginosa. Four clinical isolates and a reference strain of P. aeruginosa were employed. Combinations of fosfomycin plus polymyxin B, tobramycin or ciprofloxacin were examined over 24 h using time-kill studies (inocula ∼10(6) cfu/mL) incorporating clinically relevant concentrations (fosfomycin, 30, 150 or 300 mg/L; polymyxin B, 0.5, 1 or 2 mg/L; tobramycin, 0.5, 1.5 or 4 mg/L; ciprofloxacin, 0.5, 1 or 2.5 mg/L). Microbiological response was examined by log changes and population analysis profiles. Against susceptible isolates, monotherapy produced varying degrees of initial killing followed by rapid regrowth. Fosfomycin plus polymyxin B or tobramycin produced greater initial killing (up to ∼4 log10 cfu/mL) with many concentrations compared with monotherapy against fosfomycin-susceptible (FOF(S)) isolates. With these combinations, synergy or additivity was observed in 54 (67%) and 49 (60%) of 81 cases (nine combinations across three isolates at three timepoints) for polymyxin B and tobramycin, respectively. Substantial improvements in killing were absent against fosfomycin-resistant (FOF(R)) isolates. For fosfomycin/ciprofloxacin combinations, synergy or additivity was observed against FOF(R) isolates in 33 of 54 (61%) cases (nine combinations across two isolates at three timepoints), while improvements in killing were largely absent against FOF(S) isolates. No combination prevented emergence of fosfomycin resistance. Against P. aeruginosa, fosfomycin in combination with polymyxin B or tobramycin (FOF(S) isolates) or ciprofloxacin (FOF(R) isolates) increased bacterial killing, but did not suppress emergence of fosfomycin resistance. © The Author 2016. Published by Oxford University Press on behalf of the British Society for Antimicrobial Chemotherapy. All rights

  9. Nonproteinogenic D-amino acids at millimolar concentrations are a toxin for anaerobic microorganisms relevant to early Earth and other anoxic planets.

    Nixon, Sophie L; Cockell, Charles S


    The delivery of extraterrestrial organics to early Earth provided a potentially important source of carbon and energy for microbial life. Optically active organic compounds of extraterrestrial origin exist in racemic form, yet life on Earth has almost exclusively selected for L- over D-enantiomers of amino acids. Although D-enantiomers of proteinogenic amino acids are known to inhibit aerobic microorganisms, the role of concentrated nonproteinogenic meteoritic D-amino acids on anaerobic metabolisms relevant to early Earth and other anoxic planets such as Mars is unknown. Here, we test the inhibitory effect of D-enantiomers of two nonproteinogenic amino acids common to carbonaceous chondrites, norvaline and α-aminobutyric acid, on microbial iron reduction. Three pure strains (Geobacter bemidjiensis, Geobacter metallireducens, Geopsychrobacter electrodiphilus) and an iron-reducing enrichment culture were grown in the presence of 10 mM D-enantiomers of both amino acids. Further tests were conducted to assess the inhibitory effect of these D-amino acids at 1 and 0.1 mM. The presence of 10 mM D-norvaline and D-α-aminobutyric acid inhibited microbial iron reduction by all pure strains and the enrichment. G. bemidjiensis was not inhibited by either amino acid at 0.1 mM, but D-α-aminobutyric acid still inhibited at 1 mM. Calculations using published meteorite accumulation rates to the martian surface indicate D-α-aminobutyric acid may have reached inhibitory concentrations in little over 1000 years during peak infall. These data show that, on a young anoxic planet, the use of one enantiomer over another may render the nonbiological enantiomer an environmental toxin. Processes that generate racemic amino acids in the environment, such as meteoritic infall or impact synthesis, would have been toxic processes and could have been a selection pressure for the evolution of early racemases.

  10. The Concentration Dependence of the (Delta)s Term in the Gibbs Free Energy Function: Application to Reversible Reactions in Biochemistry

    Gary, Ronald K.


    The concentration dependence of (delta)S term in the Gibbs free energy function is described in relation to its application to reversible reactions in biochemistry. An intuitive and non-mathematical argument for the concentration dependence of the (delta)S term in the Gibbs free energy equation is derived and the applicability of the equation to…

  11. Defining serum ferritin thresholds to predict clinically relevant liver iron concentrations for guiding deferasirox therapy when MRI is unavailable in patients with non-transfusion-dependent thalassaemia.

    Taher, Ali T; Porter, John B; Viprakasit, Vip; Kattamis, Antonis; Chuncharunee, Suporn; Sutcharitchan, Pranee; Siritanaratkul, Noppadol; Origa, Raffaella; Karakas, Zeynep; Habr, Dany; Zhu, Zewen; Cappellini, Maria Domenica


    Liver iron concentration (LIC) assessment by magnetic resonance imaging (MRI) remains the gold standard to diagnose iron overload and guide iron chelation therapy in patients with non-transfusion-dependent thalassaemia (NTDT). However, limited access to MRI technology and expertise worldwide makes it practical to also use serum ferritin assessments. The THALASSA (assessment of Exjade(®) in non-transfusion-dependent THALASSemiA patients) study assessed the efficacy and safety of deferasirox in iron-overloaded NTDT patients and provided a large data set to allow exploration of the relationship between LIC and serum ferritin. Using data from screened patients and those treated with deferasirox for up to 2 years, we identified clinically relevant serum ferritin thresholds (for when MRI is unavailable) for the initiation of chelation therapy (>800 μg/l), as well as thresholds to guide chelator dose interruption (2000 μg/l). ( identifier: NCT00873041). © 2014 The Authors. British Journal of Haematology published by John Wiley & Sons Ltd.

  12. Simulations of H 2O 2 concentration profiles in the water surrounding spent nuclear fuel taking mixed radiation fields and bulk reactions into account

    Nielsen, Fredrik; Jonsson, Mats


    To simulate the dynamics of the concentration gradient of hydrogen peroxide in groundwater surrounding spent nuclear fuel under various conditions, a model has been developed. The model treats the water volume as a sequence of volume elements, and applies the processes that affect hydrogen peroxide concentration to each volume element. The surface steady-state concentrations of H 2O 2, and the time to reach steady-state, have been determined under different conditions. The processes accounted for in the model are radiolytic production of H 2O 2 from α- and β-radiation, surface reactions consuming H 2O 2, homogeneous reactions consuming H 2O 2, and diffusion. The system has been modeled mainly for different surface reaction rate constants and homogeneous (bulk) reaction rate constants. The simulations show that the surface concentration of H 2O 2 approaches the steady-state concentration very rapidly and that the impact of homogeneous (bulk) reactions consuming H 2O 2 on the steady-state concentration is significant.

  13. Quantification of Hydrogen Concentrations in Surface and Interface Layers and Bulk Materials through Depth Profiling with Nuclear Reaction Analysis.

    Wilde, Markus; Ohno, Satoshi; Ogura, Shohei; Fukutani, Katsuyuki; Matsuzaki, Hiroyuki


    Nuclear reaction analysis (NRA) via the resonant (1)H((15)N,αγ)(12)C reaction is a highly effective method of depth profiling that quantitatively and non-destructively reveals the hydrogen density distribution at surfaces, at interfaces, and in the volume of solid materials with high depth resolution. The technique applies a (15)N ion beam of 6.385 MeV provided by an electrostatic accelerator and specifically detects the (1)H isotope in depths up to about 2 μm from the target surface. Surface H coverages are measured with a sensitivity in the order of ~10(13) cm(-2) (~1% of a typical atomic monolayer density) and H volume concentrations with a detection limit of ~10(18) cm(-3) (~100 at. ppm). The near-surface depth resolution is 2-5 nm for surface-normal (15)N ion incidence onto the target and can be enhanced to values below 1 nm for very flat targets by adopting a surface-grazing incidence geometry. The method is versatile and readily applied to any high vacuum compatible homogeneous material with a smooth surface (no pores). Electrically conductive targets usually tolerate the ion beam irradiation with negligible degradation. Hydrogen quantitation and correct depth analysis require knowledge of the elementary composition (besides hydrogen) and mass density of the target material. Especially in combination with ultra-high vacuum methods for in-situ target preparation and characterization, (1)H((15)N,αγ)(12)C NRA is ideally suited for hydrogen analysis at atomically controlled surfaces and nanostructured interfaces. We exemplarily demonstrate here the application of (15)N NRA at the MALT Tandem accelerator facility of the University of Tokyo to (1) quantitatively measure the surface coverage and the bulk concentration of hydrogen in the near-surface region of a H2 exposed Pd(110) single crystal, and (2) to determine the depth location and layer density of hydrogen near the interfaces of thin SiO2 films on Si(100).

  14. Nonlinear predictive control for the concentrations profile regulation under unknown reaction disturbances in a fuel cell anode gas channel

    Luna, Julio; Ocampo-Martinez, Carlos; Serra, Maria


    In this work, a nonlinear model predictive control (NMPC) strategy is proposed to regulate the concentrations of the different gas species inside a Proton Exchange Membrane Fuel Cell (PEMFC) anode gas channel. The purpose of the regulation relies on the rejection of the unmeasurable perturbations that affect the system: the hydrogen reaction and water transport terms. The model of the anode channel is derived from the discretisation of the partial differential equations that define the nonlinear dynamics of the system, taking into account spatial variations along the channel. Forward and backward discretisations of the distributed model are employed to take advantage of the boundary conditions of the problem. A linear observer is designed and implemented to perform output-feedback control of the plant. This information is fed to the controller to regulate the states towards their desired values. Simulation results are presented to show the performance of the proposed control method over a given case study. Different cost functions are compared and the one with minimum state-regulation error is identified. Suitable dynamic responses are obtained facing the different considered disturbances.

  15. The mixture of "ecstasy" and its metabolites impairs mitochondrial fusion/fission equilibrium and trafficking in hippocampal neurons, at in vivo relevant concentrations.

    Barbosa, Daniel José; Serrat, Romàn; Mirra, Serena; Quevedo, Martí; de Barreda, Elena Goméz; Àvila, Jesús; Ferreira, Luísa Maria; Branco, Paula Sério; Fernandes, Eduarda; Lourdes Bastos, Maria de; Capela, João Paulo; Soriano, Eduardo; Carvalho, Félix


    3,4-Methylenedioxymethamphetamine (MDMA; "ecstasy") is a potentially neurotoxic recreational drug of abuse. Though the mechanisms involved are still not completely understood, formation of reactive metabolites and mitochondrial dysfunction contribute to MDMA-related neurotoxicity. Neuronal mitochondrial trafficking, and their targeting to synapses, is essential for proper neuronal function and survival, rendering neurons particularly vulnerable to mitochondrial dysfunction. Indeed, MDMA-associated disruption of Ca(2+) homeostasis and ATP depletion have been described in neurons, thus suggesting possible MDMA interference on mitochondrial dynamics. In this study, we performed real-time functional experiments of mitochondrial trafficking to explore the role of in situ mitochondrial dysfunction in MDMA's neurotoxic actions. We show that the mixture of MDMA and six of its major in vivo metabolites, each compound at 10μM, impaired mitochondrial trafficking and increased the fragmentation of axonal mitochondria in cultured hippocampal neurons. Furthermore, the overexpression of mitofusin 2 (Mfn2) or dynamin-related protein 1 (Drp1) K38A constructs almost completely rescued the trafficking deficits caused by this mixture. Finally, in hippocampal neurons overexpressing a Mfn2 mutant, Mfn2 R94Q, with impaired fusion and transport properties, it was confirmed that a dysregulation of mitochondrial fission/fusion events greatly contributed to the reported trafficking phenotype. In conclusion, our study demonstrated, for the first time, that the mixture of MDMA and its metabolites, at concentrations relevant to the in vivo scenario, impaired mitochondrial trafficking and increased mitochondrial fragmentation in hippocampal neurons, thus providing a new insight in the context of "ecstasy"-induced neuronal injury.

  16. Proton transfer reactions in the red light-activatable channelrhodopsin variant ReaChR and their relevance for its function.

    Kaufmann, Joel C D; Krause, Benjamin S; Grimm, Christiane; Ritter, Eglof; Hegemann, Peter; Bartl, Franz J


    Channelrhodopsins (ChRs) are light-gated ion channels widely used for activating selected cells in large cellular networks. ChR variants with a red-shifted absorption maximum, such as the modified Volvox carteri ChR1 red-activatable channelrhodopsin ("ReaChR," λmax = 527 nm), are of particular interest because longer wavelengths allow optical excitation of cells in deeper layers of organic tissue. In all ChRs investigated so far, proton transfer reactions and hydrogen bond changes are crucial for the formation of the ion-conducting pore and the selectivity for protons versus cations, such as Na(+), K(+), and Ca(2+) (1). By using a combination of electrophysiological measurements and UV-visible and FTIR spectroscopy, we characterized the proton transfer events in the photocycle of ReaChR and describe their relevance for its function. 1) The central gate residue Glu(130) (Glu(90) in Chlamydomonas reinhardtii (Cr) ChR2) (i) undergoes a hydrogen bond change in D → K transition and (ii) deprotonates in K → M transition. Its negative charge in the open state is decisive for proton selectivity. 2) The counter-ion Asp(293) (Asp(253) in CrChR2) receives the retinal Schiff base proton during M-state formation. Starting from M, a photocycle branching occurs involving (i) a direct M → D transition and (ii) formation of late photointermediates N and O. 3) The DC pair residue Asp(196) (Asp(156) in CrChR2) deprotonates in N → O transition. Interestingly, the D196N mutation increases 15-syn-retinal at the expense of 15-anti, which is the predominant isomer in the wild type, and abolishes the peak current in electrophysiological measurements. This suggests that the peak current is formed by 15-anti species, whereas 15-syn species contribute only to the stationary current. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

  17. Relevance of the nature of bimetallic PtAu nanoparticles as electrocatalysts for the oxygen reduction reaction in the presence of methanol

    Hernandez-Fernandez, P. [Departamento de Quimica-Fisica Aplicada, Universidad Autonoma de Madrid, Campus Cantoblanco (Spain); Instituto de Catalisis y Petroleoquimica (CSIC), C/Marie Curie 2, 28049 Madrid (Spain); Rojas, S.; Terreros, P.; Pena, M.A.; Fierro, J.L.G. [Instituto de Catalisis y Petroleoquimica (CSIC), C/Marie Curie 2, 28049 Madrid (Spain); Ocon, P.; de Frutos, A.; Figueroa, J.M. [Departamento de Quimica-Fisica Aplicada, Universidad Autonoma de Madrid, Campus Cantoblanco (Spain)


    A series of carbon supported PtAu electrocatalysts has been prepared. The performance of the samples in the methanol oxidation reaction and in the oxygen reduction reaction has been investigated by means of electrochemical techniques. The combined process, oxygen reduction reaction in the presence of methanol, has also been studied by electrochemical methods and in a single-cell. Irrespective of the performance of the samples in the oxygen reduction reaction, the ones displaying poor activity in the methanol oxidation reaction are the optimum cathode electrocatalysts for direct methanol fuel cell applications. The role of Au was found to be dependent on the actual nature of the catalyst. When alloyed, the role of Au on the methanol oxidation reaction is negligible. This is the first time that Au is being proposed as a component of methanol resistant cathode electrocatalysts. (author)

  18. Raman spectroscopy as a tool for monitoring mesoscale continuous-flow organic synthesis: Equipment interface and assessment in four medicinally-relevant reactions

    Trevor A. Hamlin


    Full Text Available An apparatus is reported for real-time Raman monitoring of reactions performed using continuous-flow processing. Its capability is assessed by studying four reactions, all involving formation of products bearing α,β-unsaturated carbonyl moieties; synthesis of 3-acetylcoumarin, Knoevenagel and Claisen–Schmidt condensations, and a Biginelli reaction. In each case it is possible to monitor the reactions and also in one case, by means of a calibration curve, determine product conversion from Raman spectral data as corroborated by data obtained using NMR spectroscopy.

  19. A kinetics study of the homogeneous and heterogeneous components of the HCl + ClONO2 reaction. [and its relevance to stratospheric chemistry

    Friedl, Randall R.; Goble, James H.; Sander, Stanley P.


    The kinetics of the reaction HCl + ClONO2 to Cl2 + HNO3 were investigated at 298 K using a flow reactor with FTIR analysis to assess the importance of this reaction for stratospheric chemistry. The observed reaction was characteristic of a heterogeneous process; an upper limit of 5 x 10 to the -18th cu cm/molecule per s was obtained for the homogeneous gas phase rate constant. From calculations of the first order wall rate constant, estimates were made of the reaction rate on stratospheric aerosols. Because both HCl and ClONO2 need to be adsorbed on the particle surface, the reaction will be of negligible importance under most stratospheric conditions.

  20. Relationship between seminal plasma zinc concentration and spermatozoa–zona pellucida binding and the ZP-induced acrosome reaction in subfertile men

    Liu, De-Yi; Sie, Boon-Shih; Liu, Ming-Li; Agresta,Franca; Baker, HW Gordon


    The aim of this study was to determine the relationship between seminal zinc concentration and spermatozoa–zona pellucida (ZP) binding and the ZP-induced acrosome reaction (ZPIAR) in subfertile men. Semen analyses and seminal zinc concentration assessments were carried out according to the World Health Organization manual for 458 subfertile men. A spermatozoa–ZP interaction test was carried out by incubating 2 × 106 motile spermatozoa with a group of four unfertilized oocytes obtained from a ...

  1. Relevance of single-particle and collective excitations in zirconium isotopes populated by neutron transfer reactions in the {sup 90}Zr+{sup 208}Pb system

    Pajtler, M. Varga, E-mail: [Department of Physics, University of Osijek, Trg Ljudevita Gaja 6, 31000 Osijek (Croatia); Szilner, S.; Malenica, D. Jelavić; Mijatović, T.; Soić, N. [Ruer Bošković Institute, HR-10001, Zagreb (Croatia); Corradi, L.; Angelis, G. de; Fioretto, E.; Montanari, D.; Stefanini, A. M.; Valiente-Dobón, J. J. [Istituto Nazionale di Fisica Nucleare, Laboratori Nazionali di Legnaro, I-35020 Legnaro (Italy); Gadea, A. [IFIC, CSIC-Universidad de Valencia, E-46071 Valencia (Spain); Haas, F. [Institut Pluridisciplinaire Hubert Curien, CNRS-IN2P3 and Université de Strasbourg, F-67037 Strasbourg (France); Lunardi, S.; Mengoni, D.; Montagnoli, G.; Recchia, F.; Scarlassara, F. [Dipartimento di Fisica, Universitá di Padova, and Istituto Nazionale di Fisica Nucleare, I-35131 Padova (Italy); Märginean, N. [Horia Hulubei National Institute of Physics and Nuclear Engineering, RO-077125 Bucharest-Magurele (Romania); Pollarolo, G. [Dipartimento di Fisica Teorica, Universitá di Torino,and Istituto Nazionale di Fisica Nucleare, I-10125 Torino (Italy); and others


    Multineutron transfer reaction {sup 90}Zr+{sup 208}Pb has been studied at the energy close to the Coulomb barrier energy by using the PRISMA + CLARA set-up. In this fragment-γ coincidence measurement, the selective properties of the reaction mechanism in the population of the specific states have been discussed. Based on the observed γ transitions of neutron transfer channels, namely {sup 89–94}Zr isotopes, their level schemes have been constructed and updated.

  2. Reaction rate of NaOCl in contact with bovine dentine: effect of activation, exposure time, concentration and pH.

    de Macedo, R.G.; Wesselink, P.R.; Zaccheo, F.; Fanali, D.; van der Sluis, L.W.M.


    Aim  To determine the influence of activation method (ultrasound or laser), concentration, pH and exposure time on the reaction rate (RR) of NaOCl when in contact with dentinal walls. Methodology  The walls from standardized root canals in bovine incisors were exposed to a standardized volume of sod

  3. H2/D2 exchange reaction on mono-disperse Pt clusters: enhanced activity from minute O2 concentrations

    Riedel, Jakob Nordheim; Rötzer, Marian David; Jørgensen, Mikkel;


    The H2/D2 exchange reaction was studied on mono-disperse Pt8 clusters in a μ-reactor. The chemical activity was studied at temperatures varying from room temperature to 180 °C using mass spectrometry. It was found that minute amounts of O2 in the gas stream increased the chemical activity...... significantly. XPS and ISS before and after reaction suggest little or no sintering during reaction. A reaction pathway is suggested based on DFT. H2 desorption is identified as the rate-limiting step and O2 is confirmed as the source of the increased activity. The binding energy of platinum atoms in a SiO2...... supported Pt8 cluster is found to be comparable to the interatomic binding energies of bulk platinum, underlining the stability of the model system....


    Ratna Dewi Kusumaningtyas


    Full Text Available The usual problem encountered on a reversible reaction is that the reaction cannot achieve a complete conversion of reactants since it is limited by the thermodynamic equilibrium. Due to this low conversion, it will face challenges with product purification and recycling of the reactants, which then cause an increase in the operation cost. To obtain higher conversion, it is necessary to shift the equilibrium towards the products by continuously removing the water formed. One popular example of reversible reaction is esterification process. In this research, water removal was conducted through an adsorption process using zeolite 4A. Effect of zeolite 4A on water concentration in the liquid phase esterification of acetic acid and 1-butanol catalyzed by sulfuric acid was investigated. It was performed in an isothermal batch reactor. The molar ratio of 1-butanol - acetic acid was 1.4 times theoretically, the catalyst concentration was 1 % wt and the mixing intensity was 1000 rpm. The influence of the temperature was studied at 40 to 80 °C and the zeolite 4A loading was varied at 1.6 to 5.52 % w/ v. The reaction was compared to the conventional esterification reaction carried out under identical conditions but without addition of zeolite 4A. Concentration of each component in the system was analyzed using on-line Gas Chromatography. Effect of removing the water produced during the reaction by using zeolite 4A was demonstrated. It was revealed that the amount of water removed was proportional to the amount of the zeolite 4A to be employed. On the other hand, the increase of the temperature led to the lower amount of water to be adsorbed. Among all the experiments, the best result was achieved on the addition of 5.52 % b/v zeolite 4A at 40 °C, where water concentration was 3.1356 g mole/L and the conversion was 76.11 % at the equilibrium condition. As comparison, water concentration on the conventional reaction performed at 40 °C was 6.9161 g mole

  5. Experimental study of the excitation functions of proton induced nuclear reactions on (167)Er for production of medically relevant (167)Tm.

    Tárkányi, F; Hermanne, A; Takács, S; Király, B; Spahn, I; Ignatyuk, A V


    (167)Tm (T(1/2)=9.25d) is a candidate radioisotope for medical therapy and diagnostics due to its Auger-electron and low-energy X- and gamma-ray emission. Excitation functions of the (167)Er(p,n)(167)Tm reaction and (168)Er(p,n)(168)Tm, (167)Er(p,2n)(166)Tm, (166)Er(p,2n)(165)Tm disturbing reactions were measured up to 15MeV by using the stacked foil irradiation technique and gamma-ray spectroscopy. The measured excitation functions agree well with the results of ALICE-IPPE, EMPIRE-II and TALYS nuclear reaction model codes. The thick target yield of (167)Tm in the 15-8MeV energy range is 6.9MBq/microAh. A short comparison of charged particle production routes of (167)Tm is given. Copyright (c) 2009 Elsevier Ltd. All rights reserved.

  6. Microscale Synthesis, Reactions, and (Super 1)H NMR Spectroscopic Investigations of Square Planar Macrocyclic, Tetramido-N Co(III) Complexes Relevant to Green Chemistry

    Watson, Tanya T.; Uffelman, Erich S.; Lee, Daniel W., III; Doherty, Jonathan R.; Schulze, Carl; Burke, Amy L.; Bonnema, Kristen, R.


    The microscale preparation, characterization, and reactivity of a square planar Co(III) complex that has grown out of a program to introduce experiments of relevance to green chemistry into the undergraduate curriculum is presented. The given experiments illustrate the remarkable redox and aqueous acid-base stability that make the macrocycles very…

  7. Relevance Theory in Translation

    Shao Jun; Jiang Min


    In perspective of relevance theory, translation is regarded as communication. According to relevance theory, communication not only requires encoding, transfer and decoding processes, but also involves inference in addition. As communication, translation decision-making is also based on the human beings' inferential mental faculty. Concentrating on relevance theory, this paper tries to analyze and explain some translation phenomena in two English versions of Cai Gen Tan-My Crude Philosophy of Life.

  8. New data on cross-sections of deuteron induced nuclear reactions on gold up to 50 MeV and comparison of production routes of medically relevant Au and Hg radioisotopes

    Tárkányi, F; Ditrói, F; Takács, S; Adam-Rebeles, R


    Investigations of cross-sections of deuteron induced nuclear reactions on gold were extended up to 50 MeV by using the standard stacked foil irradiation technique and high resolution gamma-ray spectrometry. New cross-sections are reported for the $^{197}$Au(d,xn)$^{197m,197g,195m,195g,193m,193g}$Hg and $^{197}$Au(d,x)$^{198m,198g,196m,196g,195,194}$Au nuclear reactions. The application for production of the medically relevant isotopes $^{198}$Au and $^{195m,195g,197m,197g}$Hg is discussed, including the comparison with other charged particle induced production routes. The possible use of the $^{197}$Au(d,x)$^{197m,197g,195m,193m}$Hg and $^{196m,196g}$Au reactions for monitoring deuteron beam parameters is also investigated.

  9. Theoretical Analyses and Experimental Investigations of Selective Carbothermal Reactions of Vanadium-Bearing Titanomagnetite Concentrates for Preparation of Iron-Based Wear-Resistant Material

    Zhang, Guangming; Feng, Keqin; Yue, Huifang


    Based on FACTSage® software, this paper focuses on the thermodynamic calculations of selective carbothermal reactions of vanadium-bearing titanomagnetite concentrates for preparing iron-based wear-resistant material directly from vanadium-bearing titanomagnetite concentrates. The calculations show that it was most likely to generate metallic iron, titanium carbide and vanadium carbide among all possible carbothermal reactions of vanadium-bearing titanomagnetite concentrates in a vacuum of 10 Pa. The equilibrium composition calculations indicate that Fe3O4 can be reduced to metallic iron by carbon above 400°C, FeTiO3 can be converted into TiC by carbon above 800°C and V2O5 can be converted into VC by carbon above 600°C in a vacuum of 10 Pa. The investigations demonstrated that the percentage of ferrous oxides reduced to metallic iron was about 96%, the conversion percentage of FeTiO3 into TiC was about 75% and the conversion percentage of V2O5 into VC was about 94% after the selective carbothermal reactions of vanadium-bearing titanomagnetite concentrates at 1300°C for 3 h in a vacuum of 10 Pa.

  10. Defining serum ferritin thresholds to predict clinically relevant liver iron concentrations for guiding deferasirox therapy when MRI is unavailable in patients with non‐transfusion‐dependent thalassaemia

    Taher, Ali T; Porter, John B; Viprakasit, Vip; Kattamis, Antonis; Chuncharunee, Suporn; Sutcharitchan, Pranee; Siritanaratkul, Noppadol; Origa, Raffaella; Karakas, Zeynep; Habr, Dany; Zhu, Zewen; Cappellini, Maria Domenica


    Liver iron concentration ( LIC ) assessment by magnetic resonance imaging ( MRI ) remains the gold standard to diagnose iron overload and guide iron chelation therapy in patients with non‐transfusion...

  11. Clinical relevance of the discrepancy in phenylalanine concentrations analyzed using tandem mass spectrometry compared with ion-exchange chromatography in phenylketonuria

    Bridget M. Stroup


    Conclusion: Use of DBS analyzed using MS/MS to monitor blood phe concentrations in individuals with PKU yields significantly lower phe levels compared to plasma phe levels analyzed using IEC. Optimization of current testing methodologies for measuring phe in DBS, along with patient education regarding the appropriate technique for spotting blood on filter paper is needed to improve the accuracy of using DBS to measure phe concentrations in PKU management.

  12. The NBS Reaction: A Simple Explanation for the Predominance of Allylic Substitution over Olefin Addition by Bromine at Low Concentrations.

    Wamser, Carl C.; Scott, Lawrence T.


    Examines mechanisms related to use of N-bromosuccinimide (NBS) for bromination at an allylic position. Also presents derived rate laws for three possible reactions of molecular bromine with an alkene: (1) free radical substitution; (2) free radical addition; and (3) electrophilic addition. (JN)

  13. Analysis of Blood Concentrations of Zinc, Germanium, and Lead and Relevant Environmental Factors in a Population Sample from Shandong Province, China

    Long Li


    Full Text Available Trace elements, including zinc (Zn and germanium (Ge, are essential for health; deficiency or excess levels of trace elements results is harmful. As a result of industrial and agricultural production, Pb widely exists in people’s living environment. It is absorbed mainly through the respiratory and digestive tracts, producing systemic harm. Reference values for a normal, healthy population are necessary for health assessment, prevention and treatment of related diseases, and evaluation of occupational exposures. Reference ranges for the Chinese population have not been established. From March 2009 to February 2010; we collected data and blood samples (n = 1302 from residents aged 6–60 years living in Shandong Province, China. We measured blood concentrations of Zn, Ge, and Pb using inductively coupled plasma mass spectrometry to determine reference ranges. Results were stratified by factors likely to affect the concentrations of these trace elements: sex, use of cosmetics or hair dye, age, alcohol intake, smoking habits, and consumption of fried food. The overall geometric mean (GM concentrations (95% confidence interval were 3.14 (3.08–3.20 mg/L for Zn, 19.9 (19.3–20.6 μg/L for Ge, and 24.1 (23.2–25.1 μg/L for Pb. Blood Zn concentrations were higher in women than in men (p < 0.001, while the opposite was found for Pb (p < 0.001 and sex did not influence Ge (p = 0.095. Alcohol use was associated with higher blood concentrations of Zn (p = 0.002, Ge (p = 0.002, and Pb (p = 0.001. The GM concentration of Zn was highest in 20–30-year-olds (p < 0.001, while Pb concentrations were highest in 12–16-year-olds (p < 0.001. Use of hair dye was associated with lower blood concentrations of Ge (p < 0.05. GM blood concentrations of Pb differed significantly between those who consumed fried foods 1–2 times/month (18.7 μg/L, 1–2 times/week (20.9 μg/L, and every day (28.5 μg/L; p < 0.001. Blood Pb concentrations were higher in subjects

  14. Spectra and concentration profiles throughout the reaction of curing epoxy resins from near-infrared spectroscopy and multivariate curve resolution methods.

    Larrechi, M S; Rius, F X


    When applied to near-infrared (NIR) data, multivariate curve resolution methods, in particular alternating least squares (ALS), make it possible to calculate the concentration profiles and the spectra of all species involved in the reaction of curing epoxy resins. In this paper, the model reaction between phenyl glicidyl ether and aniline (2:1) was studied at 95 degrees C. A NIR spectrum was recorded every five minutes throughout the eight-hour reaction process. The data display rank deficiency. This problem was overcome by supplying additional information to the system in the form of known spectra of some reactants. The recovered spectra and concentration profiles satisfactorily reproduced the experimental data. In this way, 99.99% of the variance associated with the experimental matrix was reproduced. A value of 0.87% was obtained for lack of fit while the similarity coefficient r between the spectra recovered and the spectra corresponding to the three pure species involved in the reaction were PGE (r = 0.994), aniline (r = 0.994), and tertiary amine (r = 0.999). The maximum and minimum limits associated with the ALS solutions were calculated, which made it possible to limit to a considerable extent the ambiguity that is characteristic of these curve resolution methods.

  15. Immediate response of Ca2+ concentration in myocardial cells against oxidation stress by extracellular photosensitization reaction using Talaporfin sodium for the arrhythmia treatment application

    Ogawa, Emiyu; Takahashi, Mei; Ito, Arisa; Arai, Tsunenori


    We studied the immediate response of myocardial cells by continuous observation using confocal microscope against oxidation stress by extracellular photosensitization reaction using Talaporfin sodium for tachyarrhythmia treatment application. Immediate response in order from several seconds to several minutes is required for the arrhythmia treatment since operators should judge the therapeutic effect during the tachyarrhythmia ablation procedure. To understand the immediate response of myocardial cells, we measured the intracellular Ca2+ concentration using fluo-4 AM during and after the extracellular photosensitization reaction. Talaporfin sodium concentration was varied 10-30 μg/ml. A red diode laser of 663 nm in wavelength was irradiated under the microscope with the radiant exposure of 40 J/cm2 and irradiance of 0.29 W/cm2. We observed the fluorescence image of fluo-4 AM each 400 ms during until 10 min after the photosensitization reaction. The myocardial cell beatings were stopped about 2 s after the beginning of the laser irradiation. The blebs were formed with the Ca2+ inflow. The intracellular Ca2+ was re-decreased after the bleb formation and then the cell necrosis was induced. The cell lethality 10 min after the laser irradiation was less than bleb formation ratio. The time response of the cell necrosis was shortened with the photosensitizer concentration increasing and the minimum average value was 209 s in the case of the 30 μg/ml in photosensitizer concentration and 40 J/cm2 in the radiant exposure. We think this extracellular photosensitization reaction may be applicable to tachyarrhythmia treatment in terms of its immediate response.

  16. Identification of key astrophysical resonances relevant for the 26g Al(p,gamma)27Si reaction in Wolf-Rayet stars, AGB stars, and classical novae.

    Lotay, G; Woods, P J; Seweryniak, D; Carpenter, M P; Janssens, R V F; Zhu, S


    A gamma-ray spectroscopy study of ;{26g}Al+p resonant states in 27Si is presented. Excitation energies were measured with improved precision and first spin-parity assignments made for excited states in 27Si above the proton threshold. The results indicate the presence of low-lying resonances with l_{p}=0 and l_{p}=2 captures that could strongly influence the ;{26g}Al(p,gamma)27Si reaction rate at low stellar temperatures, found in low-mass asymptotic giant branch (AGB), intermediate-mass AGB, super AGB, and Wolf-Rayet stars.

  17. Heavy metal accumulation in Diplodus annularis, Liza aurata, and Solea vulgaris relevant to their concentration in water and sediment from the southwestern Mediterranean (coast of Sfax).

    Ben Salem, Zohra; Ayadi, Habib


    The concentrations of heavy metals (Cd, Cu, Fe, Pb, Ni, and Zn) were measured in the liver, gills, and muscle of Solea vulgaris, Liza aurata, and Diplodus annularis, collected from the south coast of Sfax (Gabes Gulf, southwestern Mediterranean). The concentrations of heavy metals in water exhibited the following decreasing order (expressed in μg l(-1)): Fe > Ni > Zn > Cu > Pb > Cd whereas the trend is somewhat different in sediments (mg kg(-1) D.W.) Fe > Zn > Pb > Ni > Cu > Cd. The levels of heavy metals varied significantly among fish species and tissues. Heavy metal levels were found generally higher in the liver and gills than the muscle in all species. The liver was the target organ for Cd, Cu, Fe, Ni, and Zn accumulation. Nickel and lead, however, exhibited their highest concentrations in the gills. The three studied fishes showed a difference in metals accumulation decreasing in following order S. vulgaris > D. annularis > L. aurata. Solea vulgaris with the highest TFwater, TFsediment, and metal concentrations in tissues would be considered as a potential bio-indicator in the south coast of Sfax for the assessment of environmental pollution status. Comparative studies with Luza zone indicate considerable bioaccumulation of heavy metals (Pb and Zn) in the various tissues of fish samples of the south coast of Sfax.

  18. Delayed effects of environmentally relevant concentrations of 3,3',4,4'-tetrachlorobiphenyl (PCB-77) and non-polar sediment extracts detected in the prolonged-FETAX

    Gutleb, A.C.; Mossink, L.; Schriks, M.; Berg, van den J.H.J.; Murk, A.J.


    In the prolonged-FETAX (prolonged-Frog Embryo Teratogenic Assay-Xenopus) tadpoles are allowed to develop until metamorphosis after an initial 4 day early life-stage exposure (FETAX). PCB 77 (3,4,3¿,4¿-tetrachlorobiphenyl) and sediment extracts were used in the presented experiments. Concentrations o

  19. Gas-phase naphthalene concentration data recovery in ambient air and its relevance as a tracer of sources of volatile organic compounds

    Uria-Tellaetxe, Iratxe; Navazo, Marino; de Blas, Maite; Durana, Nieves; Alonso, Lucio; Iza, Jon


    Despite the toxicity of naphthalene and the fact that it is a precursor of atmospheric photooxidants and secondary aerosol, studies on ambient gas-phase naphthalene are generally scarce. Moreover, as far as we are concerned, this is the first published one using long-term hourly ambient gas-phase naphthalene concentrations. In this work, it has been also demonstrated the usefulness of ambient gas-phase naphthalene to identify major sources of volatile organic compounds (VOC) in complex scenarios. Initially, in order to identify main benzene emission sources, hourly ambient measurements of 60 VOC were taken during a complete year together with meteorological data in an urban/industrial area. Later, due to the observed co-linearity of some of the emissions, a procedure was developed to recover naphthalene concentration data from recorded chromatograms to use it as a tracer of the combustion and distillation of petroleum products. The characteristic retention time of this compound was determined comparing previous GC-MS and GC-FID simultaneous analysis by means of relative retention times, and its concentration was calculated by using relative response factors. The obtained naphthalene concentrations correlated fairly well with ethene (r = 0.86) and benzene (r = 0.92). Besides, the analysis of daily time series showed that these compounds followed a similar pattern, very different from that of other VOC, with minimum concentrations at day-time. This, together with the results from the assessment of the meteorological dependence pointed out a coke oven as the major naphthalene and benzene emitting sources in the study area.

  20. On the relevance of the H2 + O reaction pathway for the surface formation of interstellar water - A combined experimental and modeling study

    Lamberts, Thanja; Fedoseev, Gleb; Ioppolo, Sergio; Chuang, Ko-Ju; Linnartz, Harold


    The formation of interstellar water has been commonly accepted to occur on the surfaces of icy dust grains in dark molecular clouds at low temperatures (10-20 K), involving hydrogenation reactions of oxygen allotropes. As a result of the large abundances of molecular hydrogen and atomic oxygen in these regions, the reaction H2 + O has been proposed to contribute significantly to the formation of water as well. However, gas phase experiments and calculations, as well as solid-phase experimental work contradict this hypothesis. Here, we use precisely executed temperature programmed desorption (TPD) experiments in an ultra-high vacuum setup combined with kinetic Monte Carlo simulations to establish an upper limit of the water production starting from H2 and O. These reactants are brought together in a matrix of CO2 in a series of (control) experiments at different temperatures and with different isotopological compositions. The amount of water detected with the quadrupole mass spectrometer upon TPD is found to o...

  1. Properties of resonant states in 18Ne relevant to key 14O(alpha,p)17F breakout reaction in type I x-ray bursts

    Hu, J; Parikh, A; Xu, S W; Yamaguchi, H; Kahl, D; Ma, P; Su, J; Wang, H W; Nakao, T; Wakabayashi, Y; Teranishi, T; Hahn, K I; Moon, J Y; Sung, H S; Hashimoto, T; Chen, A A; Irvine, D; Lee, C S; Kubono, S


    The $^{14}$O($\\alpha$,$p$)$^{17}$F reaction is one of the key reactions involved in the breakout from the hot-CNO cycle to the rp-process in type I x-ray bursts. The resonant properties in the compound nucleus $^{18}$Ne have been investigated through resonant elastic scattering of $^{17}$F+$p$. The radioactive $^{17}$F beam was separated by the CNS Radioactive Ion Beam separator (CRIB) and bombarded a thick H$_2$ gas target at 3.6 MeV/nucleon. The recoiling light particles were measured by using three ${\\Delta}$E-E silicon telescopes at laboratory angles of $\\theta$$_{lab}$$\\approx$3$^\\circ$, 10$^\\circ$ and 18$^\\circ$, respectively. Five resonances at $E_{x}$=6.15, 6.28, 6.35, 6.85, and 7.05 MeV were observed in the excitation functions. Based on an $R$-matrix analysis, $J^{\\pi}$=1$^-$ was firmly assigned to the 6.15-MeV state. This state dominates the thermonuclear $^{14}$O($\\alpha$,$p$)$^{17}$F rate below 1 GK. We have also confirmed the existence and spin-parities of three states between 6.1 and 6.4 MeV. A...

  2. HIV treatments reduce malaria liver stage burden in a non-human primate model of malaria infection at clinically relevant concentrations in vivo.

    Charlotte V Hobbs

    Full Text Available We have previously shown that the HIV protease inhibitor lopinavir-ritonavir (LPV-RTV and the antibiotic trimethoprim sulfamethoxazole (TMP-SMX inhibit Plasmodium liver stages in rodent malarias and in vitro in P. falciparum. Since clinically relevant levels are better achieved in the non-human-primate model, and since Plasmodium knowlesi is an accepted animal model for the study of liver stages of malaria as a surrogate for P. falciparum infection, we investigated the antimalarial activity of these drugs on Plasmodium knowlesi liver stages in rhesus macaques. We demonstrate that TMP-SMX and TMP-SMX+LPV-RTV (in combination, but not LPV-RTV alone, inhibit liver stage parasite development. Because drugs that inhibit the clinically silent liver stages target parasites when they are present in lower numbers, these results may have implications for eradication efforts.

  3. Microfluidic fabrication of polymersomes enclosing an active Belousov-Zhabotinsky (BZ) reaction: Effect on their stability of solute concentrations in the external media.

    Hu, Yuandu; Pérez-Mercader, Juan


    Core/shell double emulsions were fabricated using glasscapillary based microfluidic techniques. Poly(butadiene) 46-bpoly(ethylene oxide)30 in mixture with cyclo-hexane/chloroform were contained as the shell part of droplets, whose core part was the full 1,4-cyclohexadiene based Belousov-Zhabotinsky reaction solution of unknown osmolality. The droplets were collected in solutions of both low and relatively high concentrations of salt. This resulted in the respective increase or decrease of the core part diameter. In both cases, after an incubation period, the droplets eventually evolved into polymer vesicles. In solutions with low concentration of salt, the droplets evolved into polymer vesicles after the evaporation of the vola-tile solvent contained in the shell part. Due to the dewetting of the shell and core parts,droplets in solutions of relatively high salt concentration evolved into polymer vesicles only after three days of incubation. The dewetted shell part displayed crescent-moon-shapes with different curvatures. The final diameter of the vesicles differed from the diameter of the initial core droplets. We demonstrate that vesicles with unknown osmolality core parts are formed in both solutions of very low or relatively high concentration of salt; furthermore, we also demonstrate that they follow different formation pathways. In the appropriate conditions, the vesicles experienced a form of "collapsing" behavior due to the activity of the entrapped chemical reaction.

  4. Reduction Kinetics of Magnetite Concentrate Particles with Hydrogen at 1150-1600 °C Relevant to a Novel Flash Ironmaking Process

    Elzohiery, Mohamed; Mohassab, Yousef; Abdelghany, Amr; Zhang, Shengqin; Chen, Feng; Sohn, Hong Yong

    A novel ironmaking process is under development at the University of Utah aimed at producing iron directly from iron oxide concentrate in a flash reactor. This process will reduce hazardous emissions and save energy. The kinetics of magnetite reduction with hydrogen was previously investigated in our laboratory in the temperature range 1150 to 1400 °C at large temperature increments ( 100 °C increments). Due to the significant melting that occurs above 1350 °C, the reduction kinetics was measured and analyzed in two distinct temperature ranges of 1150 to 1350 °C and 1350 to 1600 °C ( 50 °C increments). Experiments were performed using magnetite concentrate particles of different sizes under various hydrogen partial pressures and residence times. Reduction degrees of more than 90 % were achieved in a few seconds at temperatures as low as 1250 °G Different rate expressions were needed to obtain reliable agreement with experimental data.

  5. The mixture of "ecstasy" and its metabolites is toxic to human SH-SY5Y differentiated cells at in vivo relevant concentrations.

    Barbosa, Daniel José; Capela, João Paulo; Silva, Renata; Vilas-Boas, Vânia; Ferreira, Luísa Maria; Branco, Paula Sério; Fernandes, Eduarda; Bastos, Maria de Lourdes; Carvalho, Félix


    The neurotoxicity of "ecstasy" (3,4-methylenedioxymethamphetamine, MDMA) is thought to involve hepatic metabolism, though its real contribution is not completely understood. Most in vitro neurotoxicity studies concern isolated exposures of MDMA or its metabolites, at high concentrations, not considering their mixture, as expected in vivo. Therefore, our postulate is that combined deleterious effects of MDMA and its metabolites, at low micromolar concentrations that may be attained into the brain, may elicit neurotoxicity. Using human SH-SY5Y differentiated cells as dopaminergic neuronal model, we studied the neurotoxicity of MDMA and its MDMA metabolites α-methyldopamine and N-methyl-α-methyldopamine and their correspondent glutathione and N-acetylcysteine monoconjugates, under isolated exposure and as a mixture, at normothermic or hyperthermic conditions. The results showed that the mixture of MDMA and its metabolites was toxic to SH-SY5Y differentiated cells, an effect potentiated by hyperthermia and prevented by N-acetylcysteine. As a mixture, MDMA and its metabolites presented a different toxicity profile, compared to each compound alone, even at equimolar concentrations. Caspase 3 activation, increased reactive oxygen species production, and intracellular Ca(2+) raises were implicated in the toxic effect. The mixture increased intracellular glutathione levels by increasing its de novo synthesis. In conclusion, this study demonstrated, for the first time, that the mixture of MDMA and its metabolites, at low micromolar concentrations, which represents a more realistic approach of the in vivo scenario, elicited toxicity to human SH-SY5Y differentiated cells, thus constituting a new insight into the context of MDMA-related neurotoxicity.

  6. Temperature Dependence of Carbon Kinetic Isotope Effect for the Oxidation Reaction of Ethane by Hydroxyl Radicals Under Atmospherically Relevant Conditions: Experimental and Theoretical Studies

    Piansawan, Tammarat


           Ethane is the second most abundant hydrocarbon in the atmosphere, after methane, impacting on air quality, human health and climate. A quantification of its effects requires accurate knowledge of sources, processes along transport, and sinks. Carbon stable isotopic ratio investigations, complementarily to concentration measurements, were demonstrated to give more insight in source apportionment and atmospheric processing of organic compounds.        Yet, apportionment of atmospher...

  7. New $\\alpha$ ANC measurement of the 1/2$^+$ state in $^{17}$O at 6.356 MeV, that dominates the $^{13}$C($\\alpha$,n)$^{16}$O reaction rate at temperatures relevant for the s-process

    Avila, M L; Koshchiy, E; Baby, L T; Belarge, J; Kemper, K W; Kuchera, A N; Santiago-Gonzalez, D


    Background: Accurate knowledge of the $^{13}$C($\\alpha$,$n$)$^{16}$O reaction cross section is important for the understanding of the s-process in AGB stars, since it is considered to be the main source of neutrons. The sub-threshold 1/2$^+$ state at excitation energy of 6.356 MeV in $^{17}$O has a strong influence on the reaction cross section at energies relevant for astrophysics. Several experiments have been performed to determine the contribution of this state to the $^{13}$C($\\alpha,n)^{16}$O reaction rate. Nevertheless, significant discrepancies between different measurements remain. Purpose: The aim of this work is to investigate these discrepancies. Method: An 8 MeV $^{13}$C beam (below the Coulomb barrier) was used to study the $\\alpha$-transfer reaction $^6$Li($^{13}$C,$d$)$^{17}$O. Results: The squared Coulomb modified ANC of the 1/2$^+$ state in $^{17}$O measured in this work is $(\\tilde C^{^{17}\\text{O}(1/2+)}_{\\alpha-^{13}\\text{C}})^2=3.6\\pm0.7\\hspace{0.2cm}\\text{fm}^{-1}$. Conclusions: Discrep...

  8. Investigations on the effect of antioxidant type and concentration and model system matrix on acrylamide formation in model Maillard reaction systems.

    Constantinou, Costas; Koutsidis, Georgios


    The formation of acrylamide in model Maillard reaction systems containing phenolic compounds was examined, with regards to phenolic type, concentration, and model system matrix. In dry glyoxal/asparagine waxy maize starch (WMS) systems, 9 out of 10 examined phenolics demonstrated an inhibiting effect, with the most significant reductions (55-60%) observed for caffeoylquinic acids. In WMS glucose/asparagine systems, examination of three different concentrations (0.1, 0.5 and 1 μmol/g WMS) suggested a 'minimum effective concentration' for epicatechin and caffeic acid, whilst addition of caffeoylquinic acids resulted in dose-dependent acrylamide reduction (25-75%). The discordant results of further studies utilising different matrices (dry and wet-to-dry) indicated that, apart from the nature and chemical reactivity, the matrix and the physical state of the reactants might be important for acrylamide formation.

  9. Kinetics of reaction of roasting of soda ash and ilmenite ore concentrate for formation of sodium titanates

    Nafeaa I.A.


    Full Text Available Alkaline metals and hydrogen titanates are of great interest for possible applications. The soda ash and Rosetta ilmenite ore concentrate briquette were investigated. The kinetic of formation of sodium titanate was studied in the temperature range 700°C to 900°C.

  10. Inflammatory reactions in placental blood of Plasmodium falciparum-infected women and high concentrations of soluble E-selectin and a circulating P. falciparum protein in the cord sera

    Jakobsen, P H; Rasheed, F N; Bulmer, J N


    concentrations measured in the placenta. Markers of inflammatory reactions: IL-10, sIL-2R, sIL-4R, and soluble tumour necrosis factor receptor I (sTNF-RI) were found in high concentrations in the placenta, indicating that inflammatory reactions take place in the placenta which has been regarded...

  11. At clinically relevant concentrations the anaesthetic/amnesic thiopental but not the anticonvulsant phenobarbital interferes with hippocampal sharp wave-ripple complexes

    Papatheodoropoulos, Costas; Sotiriou, Evangelos; Kotzadimitriou, Dimitrios; Drimala, Panagiota


    Background Many sedative agents, including anesthetics, produce explicit memory impairment by largely unknown mechanisms. Sharp-wave ripple (SPW-R) complexes are network activity thought to represent the neuronal substrate for information transfer from the hippocampal to neocortical circuits, contributing to the explicit memory consolidation. In this study we examined and compared the actions of two barbiturates with distinct amnesic actions, the general anesthetic thiopental and the anticonvulsant phenobarbital, on in vitro SPW-R activity. Results Using an in vitro model of SPW-R activity we found that thiopental (50–200 μM) significantly and concentration-dependently reduced the incidence of SPW-R events (it increased the inter-event period by 70–430 %). At the concentration of 25 μM, which clinically produces mild sedation and explicit memory impairment, thiopental significantly reduced the quantity of ripple oscillation (it reduced the number of ripples and the duration of ripple episodes by 20 ± 5%, n = 12, P Phenobarbital significantly accelerated SPWs at 50 and 100 μM whereas it reduced their rate at 200 and 400 μM. Furthermore, it significantly prolonged SPWs, reduced their synchrony and reduced the quantity of ripples only at the clinically very high concentration of 400 μM, reported to affect memory. Conclusion We hypothesize that thiopental, by interfering with SPW-R activity, through enhancement of the GABAA receptor-mediated transmission, affects memory processes which involve hippocampal circuit activation. The quantity but not the frequency of ripple oscillation was affected by the drug. PMID:17672909

  12. Effect of Hydrogen Peroxide Concentration in Remediation of Oil-contaminated Soils with Use of Fenton Reaction

    A. S. Yousefi


    Full Text Available Refining oil-contaminated soils has a great importance especially in oil producer countries such as Iran. Different methods have been provided to eliminate oil contaminations from soil. The aim of this study was to investigate the effect of Hydrogen peroxide concentration in refining oil-contaminated soils with Fenton chemical method. To do this, a calcareous soil complex sample was collected around the Tehran oil refinery and treated with 10 and 20 percent petroleum in three replications. After reaching to balance conditions, the sample was treated using0.01, 0.02,0.12,0.24,0.47 and 0.71 equivalent of Hydrogen peroxide. The results indicated that in all level of H2O2, the eliminating efficiency in 10 percent was more than 20 percent treatment. Also a significant difference between the levels of hydrogen peroxide used in the removal of oil pollution in both surface concentrations was obtained (P<0.01.

  13. At clinically relevant concentrations the anaesthetic/amnesic thiopental but not the anticonvulsant phenobarbital interferes with hippocampal sharp wave-ripple complexes

    Sotiriou Evangelos


    Full Text Available Abstract Background Many sedative agents, including anesthetics, produce explicit memory impairment by largely unknown mechanisms. Sharp-wave ripple (SPW-R complexes are network activity thought to represent the neuronal substrate for information transfer from the hippocampal to neocortical circuits, contributing to the explicit memory consolidation. In this study we examined and compared the actions of two barbiturates with distinct amnesic actions, the general anesthetic thiopental and the anticonvulsant phenobarbital, on in vitro SPW-R activity. Results Using an in vitro model of SPW-R activity we found that thiopental (50–200 μM significantly and concentration-dependently reduced the incidence of SPW-R events (it increased the inter-event period by 70–430 %. At the concentration of 25 μM, which clinically produces mild sedation and explicit memory impairment, thiopental significantly reduced the quantity of ripple oscillation (it reduced the number of ripples and the duration of ripple episodes by 20 ± 5%, n = 12, P P P Conclusion We hypothesize that thiopental, by interfering with SPW-R activity, through enhancement of the GABAA receptor-mediated transmission, affects memory processes which involve hippocampal circuit activation. The quantity but not the frequency of ripple oscillation was affected by the drug.

  14. Concentrations of polybrominated diphenyl ethers (PBDEs) in central air-conditioner filter dust and relevance of non-dietary exposure in occupational indoor environments in Greece.

    Besis, Athanasios; Katsoyiannis, Athanasios; Botsaropoulou, Elisavet; Samara, Constantini


    Polybrominated Diphenyl Ethers (PBDEs) are ubiquitous in the indoor environment owing to their use in consumer products and various studies around the world have found higher concentrations indoors than outdoors. Central air conditioner (A/C) systems have been widely used in many workplaces, therefore, studying of PBDEs in central A/C filter dust is useful to better understand the occurrences and health implications of PBDEs in indoor environments. The present study examined the occurrence of PBDEs in central A/C filter dust collected from various workplaces (n = 20) in Thessaloniki, Greece. The sum concentrations of 21 target congeners (∑21PBDE) in A/C dust ranged between 84 and 4062 ng g(-1) with a median value of 1092 ng g(-1), while BDE-209 was found to be the most abundant BDE congener. The daily intake via dust ingestion of PBDEs estimated for the employees of the occupational settings ranged from 3 to 45 ng day(-1) (median 12 ng day(-1)).

  15. Telecommunication Support System Using Keywords and Their Relevant Information in Videoconferencing — Presentation Method for Keeping Audience's Concentration at Distance Lectures

    Asai, Kikuo; Kondo, Kimio; Kobayashi, Hideaki; Saito, Fumihiko

    We developed a prototype system to support telecommunication by using keywords selected by the speaker in a videoconference. In the traditional presentation style, a speaker talks and uses audiovisual materials, and the audience at remote sites looks at these materials. Unfortunately, the audience often loses concentration and attention during the talk. To overcome this problem, we investigate a keyword presentation style, in which the speaker holds keyword cards that enable the audience to see additional information. Although keyword captions were originally intended for use in video materials for learning foreign languages, they can also be used to improve the quality of distance lectures in videoconferences. Our prototype system recognizes printed keywords in a video image at a server, and transfers the data to clients as multimedia functions such as language translation, three-dimensional (3D) model visualization, and audio reproduction. The additional information is collocated to the keyword cards in the display window, thus forming a spatial relationship between them. We conducted an experiment to investigate the properties of the keyword presentation style for an audience. The results suggest the potential of the keyword presentation style for improving the audience's concentration and attention in distance lectures by providing an environment that facilitates eye contact during videoconferencing.

  16. Effect of Hydrogen Peroxide Concentration in Remediation of Oil-contaminated Soils with Use of Fenton Reaction

    A. S. Yousefi; A. Bostani


    Refining oil-contaminated soils has a great importance especially in oil producer countries such as Iran. Different methods have been provided to eliminate oil contaminations from soil. The aim of this study was to investigate the effect of Hydrogen peroxide concentration in refining oil-contaminated soils with Fenton chemical method. To do this, a calcareous soil complex sample was collected around the Tehran oil refinery and treated with 10 and 20 percent petroleum in three replications. Af...

  17. The Structure of Ca2+ Sensor Case16 Reveals the Mechanism of Reaction to Low Ca2+ Concentrations

    Lydia A. Strukova


    Full Text Available Here we report the first crystal structure of a high-contrast genetically encoded circularly permuted green fluorescent protein (cpGFP-based Ca2+ sensor, Case16, in the presence of a low Ca2+ concentration. The structure reveals the positioning of the chromophore within Case16 at the first stage of the Ca2+-dependent response when only two out of four Ca2+-binding pockets of calmodulin (CaM are occupied with Ca2+ ions. In such a “half Ca2+-bound state”, Case16 is characterized by an incomplete interaction between its CaM-/M13-domains. We also report the crystal structure of the related Ca2+ sensor Case12 at saturating Ca2+ concentration. Based on this structure, we postulate that cpGFP-based Ca2+ sensors can form non-functional homodimers where the CaM-domain of one sensor molecule binds symmetrically to the M13-peptide of the partner sensor molecule. Case12 and Case16 behavior upon addition of high concentrations of free CaM or M13-peptide reveals that the latter effectively blocks the fluorescent response of the sensor. We speculate that the demonstrated intermolecular interaction with endogenous substrates and homodimerization can impede proper functioning of this type of Ca2+ sensors in living cells.

  18. Relevance of the synthesis route of Se-modified Ru/C as methanol tolerant electrocatalysts for the oxygen reduction reaction

    Montiel, M.; Hernandez-Fernandez, P.; Fatas, E.; Ocon, P. [Departamento de Quimica Fisica Aplicada (CII), Universidad Autonoma de Madrid, Madrid (Spain); Garcia-Rodriguez, S.; Rojas, S.; Fierro, J.L. Ga [Instituto de Catalisis y Petroleoquimica, CSIC, C/Marie Curie 2, 8049 Madrid (Spain); Diaz, R. [Departamento de Fisica Aplicada (CXII), Universidad Autonoma de Madrid, Madrid (Spain)


    A series of Se-modified Ru/C (Se-Ru/C) samples were prepared from a carbon-supported ruthenium precursor. Selenium was incorporated by two different methods; in the first case, Se was incorporated by treating the Ru/C precursor in a selenious acid solution followed by reduction in H{sub 2} atmosphere. In the second case, Se was incorporated to Ru/C by means of thermal treatment in a selenium atmosphere. The samples thus obtained were characterized by different techniques: X-ray diffraction, energy dispersive X-ray spectroscopy, transmission electron microscopy and X-ray photoelectron spectroscopy. A detailed study has been made of the structural properties and chemical composition of the different Se-Ru/C samples. Microscopy results reveal that Se is incorporated homogeneously, being preferentially located on the surface of the Ru atoms. These results agree well with XRD and XPS data. The incorporation of Se in the lattice results in the formation of RuSe{sub 2} only if RuO{sub 2} already exists. On the contrary, if Ru is in its metallic form, Se remains as an amorphous layer located on the surface of the Ru particles. The performance of the catalysts on the oxygen reduction reaction was evaluated either in the absence and presence of methanol. Se-containing samples develop more active and methanol tolerant catalysts, particularly when Se is located on the surface of the Ru particles. (author)

  19. Shell-model study of 31S at excitations relevant to the thermonuclear 30P(p,γ)31S reaction rate

    Bouhelal, M.; Haas, F.


    Recent experimental data about the 30P(p, γ) reaction have been reported, where a list of confirmed 31S excited states within 500 keV of the 30P(p, γ)31S threshold at Ex = 6131 keV and their properties were studied. Definitive constraints on J^{π} are only given for two levels; the other ones are either tentative (five states) or undefined (six states). In order to confirm the proposed spin/parity assignments and to determine the unknown ones a comparison with shell-model calculations is crucial. We have performed a shell-model calculation using the (0+1)hbarω PSDPF interaction to calculate the excitation energy spectrum of mass 31 ( 31S - 31P up to 7000 keV. Between 6100 and 6700 keV, an excitation energy region of astrophysical interest, we obtain a set of negative-parity states that are good candidates for the observed ones. A complete spectrum of positive- and negative-parity states can now be proposed based also on a comparison with the 31P spectrum up to 7000 keV.

  20. Relevance of the synthesis route of Se-modified Ru/C as methanol tolerant electrocatalysts for the oxygen reduction reaction

    Montiel, M.; García-Rodríguez, S.; Hernández-Fernández, P.; Díaz, R.; Rojas, S.; Fierro, J. L. Gª; Fatás, E.; Ocón, P.

    A series of Se-modified Ru/C (Se-Ru/C) samples were prepared from a carbon-supported ruthenium precursor. Selenium was incorporated by two different methods; in the first case, Se was incorporated by treating the Ru/C precursor in a selenious acid solution followed by reduction in H 2 atmosphere. In the second case, Se was incorporated to Ru/C by means of thermal treatment in a selenium atmosphere. The samples thus obtained were characterized by different techniques: X-ray diffraction, energy dispersive X-ray spectroscopy, transmission electron microscopy and X-ray photoelectron spectroscopy. A detailed study has been made of the structural properties and chemical composition of the different Se-Ru/C samples. Microscopy results reveal that Se is incorporated homogeneously, being preferentially located on the surface of the Ru atoms. These results agree well with XRD and XPS data. The incorporation of Se in the lattice results in the formation of RuSe 2 only if RuO 2 already exists. On the contrary, if Ru is in its metallic form, Se remains as an amorphous layer located on the surface of the Ru particles. The performance of the catalysts on the oxygen reduction reaction was evaluated either in the absence and presence of methanol. Se-containing samples develop more active and methanol tolerant catalysts, particularly when Se is located on the surface of the Ru particles.

  1. Optimization of the elution buffer and concentration method for detecting hepatitis E virus in swine liver using a nested reverse transcription-polymerase chain reaction and real-time reverse transcription-polymerase chain reaction.

    Son, Na Ry; Seo, Dong Joo; Lee, Min Hwa; Seo, Sheungwoo; Wang, Xiaoyu; Lee, Bog-Hieu; Lee, Jeong-Su; Joo, In-Sun; Hwang, In-Gyun; Choi, Changsun


    The aim of this study was to develop an optimal technique for detecting hepatitis E virus (HEV) in swine livers. Here, three elution buffers and two concentration methods were compared with respect to enhancing recovery of HEV from swine liver samples. Real-time reverse transcription-polymerase chain reaction (RT-PCR) and nested RT-PCR were performed to detect HEV RNA. When phosphate-buffered saline (PBS, pH 7.4) was used to concentrate HEV in swine liver samples using ultrafiltration, real-time RT-PCR detected HEV in 6 of the 26 samples. When threonine buffer was used to concentrate HEV using polyethylene glycol (PEG) precipitation and ultrafiltration, real-time RT-PCR detected HEV in 1 and 3 of the 26 samples, respectively. When glycine buffer was used to concentrate HEV using ultrafiltration and PEG precipitation, real-time RT-PCR detected HEV in 1 and 3 samples of the 26 samples, respectively. When nested RT-PCR was used to detect HEV, all samples tested negative regardless of the type of elution buffer or concentration method used. Therefore, the combination of real-time RT-PCR and ultrafiltration with PBS buffer was the most sensitive and reliable method for detecting HEV in swine livers. Copyright © 2014 Elsevier B.V. All rights reserved.

  2. Benzalkonium chloride (BAC) and dimethyldioctadecyl-ammonium bromide (DDAB), two common quaternary ammonium compounds, cause genotoxic effects in mammalian and plant cells at environmentally relevant concentrations.

    Ferk, F; Misík, M; Hoelzl, C; Uhl, M; Fuerhacker, M; Grillitsch, B; Parzefall, W; Nersesyan, A; Micieta, K; Grummt, T; Ehrlich, V; Knasmüller, S


    Quaternary ammonium compounds (QACs) are cationic surfactants that are widely used as disinfectants. In the present study, we tested two important representatives, namely, benzalkonium chloride (BAC) and dimethyldioctadecyl-ammonium bromide (DDAB) in four genotoxicity tests, namely, in the Salmonella/microsome assay with strains TA 98, TA 100 and TA 102, in the single-cell gel electrophoresis (SCGE) assay with primary rat hepatocytes and in micronucleus (MN) assays with peripheral human lymphocytes and with root tip cells of Vicia faba. In the bacterial experiments, consistently negative results were obtained in the dose range between 0.001 and 110 microg per plate in the presence and absence of metabolic activation while significant induction of DNA migration was detected in the liver cells. With BAC, a moderate but significant effect was found with an exposure concentration of 1.0 mg/l while DDAB caused damage at lower doses (0.3 mg/l). The effects were not altered when the nuclei were treated with formamidopyridine glycosylase, indicating that they are not due to formation of oxidized purines. The MN assays with blood cells were carried out under identical conditions to the SCGE experiments and a significant increase was seen at the highest dose levels (BAC: 1.0 and 3.0 mg/l; DDAB: 1 mg/l). Both compounds also caused significant induction of MN as well as inhibition of cell division in plant cells, the lowest effective levels were 1.0 and 10 mg/l for DDAB and BAC, respectively. Our findings show that both chemicals induce moderate but significant genotoxic effects in eukaryotic cells at concentrations which are found in wastewaters and indicate that their release into the environment may cause genetic damage in exposed organisms. Furthermore, the direct contact of humans to QAC-containing detergents and pharmaceuticals that contain substantially higher concentrations than those which were required to cause effects in eukaryotic cells in the present study should


    Dutuit, Odile; Thissen, Roland; Vuitton, Veronique [Institut de Planetologie et d' Astrophysique de Grenoble, UJF-Grenoble 1/CNRS-INSU, UMR 5274, F-38041 Grenoble (France); Carrasco, Nathalie [Laboratoire Atmospheres, Milieux, Observations Spatiales, CNRS, UVSQ/UPMC, F-78280 Guyancourt (France); Alcaraz, Christian; Pernot, Pascal [Laboratoire de Chimie Physique, CNRS/UPS UMR 8000, Bat.349, F-91405 Orsay Cedex (France); Balucani, Nadia; Casavecchia, Piergiorgio [Dipartimento di Chimica, Universita degli Studi di Perugia, Via Elce di Sotto, 8, I-06123 Perugia (Italy); Canosa, Andre; Picard, Sebastien Le [Departement de Physique Moleculaire, Universite de Rennes 1, Institut de Physique de Rennes, UMR 6251 CNRS Universite, Campus de Beaulieu-Bat 11C, F-35042 Rennes Cedex (France); Loison, Jean-Christophe [Institut des Sciences Moleculaires, Universite Bordeaux 1/CNRS, UMR 5255, 351 cours de la Liberation, F-33405 Talence Cedex (France); Herman, Zdenek; Zabka, Jan [J. Heyrovsky Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, Dolejskova 3 CZ-182 23 Prague 8 (Czech Republic); Ascenzi, Daniela; Tosi, Paolo [Dipartimento di Fisica, Universita di Trento, Via Sommarive 14, I-38123 Trento (Italy); Franceschi, Pietro [Biostatistics and Data Management, IASMA Research and Innovation Centre, Fondazione E. Mach, Via E. Mach, 1 I-38010 S. Michele all' Adige (Italy); Price, Stephen D. [Department of Chemistry, UCL, Christopher Ingold Laboratories, 20 Gordon Street, London WC1H 0AJ (United Kingdom); Lavvas, Panayotis, E-mail: [Groupe de Spectrometrie Moleculaire et Atmospherique, CNRS, UMR 6089, Campus Moulin de la Housse-BP 1039, Universite Reims Champagne-Ardenne, F-51687 Reims (France)


    This paper is a detailed critical review of the production processes and reactions of N, N{sup +}, N{sup +} {sub 2}, N{sup ++}, and N{sup ++} {sub 2} of relevance to Titan's atmosphere. The review includes neutral, ion-molecule, and recombination reactions. The review covers all possible active nitrogen species under Titan's atmospheric conditions, specifically N{sub 2} (A {sup 3}{Sigma}{sup +} {sub u}), N ({sup 4} S), N ({sup 2} D), N ({sup 2} P), N{sup +} {sub 2}, N{sup +} ({sup 3} P), N{sup +} ({sup 1} D), N{sup ++} {sub 2}, and N{sup ++} species, and includes a critical survey of the reactions of N, N{sup +}, N{sup +} {sub 2}, N{sup ++}, and N{sup ++} {sub 2} with N{sub 2}, H{sub 2}, D{sub 2}, CH{sub 4}, C{sub 2}H{sub 2}, C{sub 2}H{sub 4}, C{sub 2}H{sub 6}, C{sub 3}H{sub 8} and the deuterated hydrocarbon analogs, as well as the recombination reactions of N{sup +} {sub 2}, N{sup +}, N{sup ++} {sub 2}, and N{sup ++}. Production processes, lifetimes, and quenching by collisions with N{sub 2} of all reactant species are reviewed. The N ({sup 4} S) state is reactive with radicals and its reactions with CH{sub 2}, CH{sub 3}, C{sub 2}H{sub 3}, and C{sub 2}H{sub 5} are reviewed. Metastable states N{sub 2} (A {sup 3}{Sigma}{sup +} {sub u}), N ({sup 2} D), and N ({sup 2} P) are either reactive or quenched by collisions with the target molecules reviewed. The reactions of N{sup +} ({sup 1} D) have similar rate constants as N{sup +} ({sup 3} P), but the product branching ratios differ significantly. Temperature effects and the role of the kinetic energy content of reactants are investigated. In all cases, experimental uncertainties of laboratory data are reported or estimated. Recommended values with uncertainties, or estimated values when no data are available, are given for rate constants and product branching ratios at 300 K and at the atmospheric temperature range of Titan (150-200 K for neutral reactions and 150 K for ion reactions).

  4. The effect of Na concentration on the kinetic phase transitions of a monomer-dimer reaction system on Na-promoted surface

    Khan, K.M.; Basit, A. [Nuclear Physics Division, Pakistan Institute of Nuclear Science and Technology (PINSTECH), Islamabad (Pakistan); Albano, E.V. [Research Institute of Theoretical and Applied Physical Chemistry (INIFTA), CONICET, UNLP, CIC, La Plata (Argentina)


    A simple lattice-gas model for the reaction of CO and NO on an Na-modified surface of a square lattice is studied. The crucial property of the model is Na-induced dissociation of NO, which triggers the catalytic reaction. Some interesting features are added to the phase diagram when the range of Na-induced NO dissociation is studied in the nearest and the next-nearest neighbourhood. The moment CO partial pressure (y{sub CO}) departs from zero, the continuous production of CO{sub 2} and N{sub 2} starts. This production remains continuous until a point where the catalytic activity stops and the surface is poisoned with a combination of CO, N and O. The value of poisoning point depends upon the value of Na concentration on the surface. (author)

  5. Effects of SULT1A1 Copy Number Variation on Estrogen Concentration and Tamoxifen-Associated Adverse Drug Reactions in Premenopausal Thai Breast Cancer Patients: A Preliminary Study.

    Charoenchokthavee, Wanaporn; Ayudhya, Duangchit Panomvana Na; Sriuranpong, Virote; Areepium, Nutthada


    Tamoxifen is a pharmacological estrogen inhibitor that binds to the estrogen receptor (ER) in breast cells. However, it shows an estrogenic effect in other organs, which causes adverse drug reactions (ADRs). The sulfotransferase 1A1 (SULT1A1) enzyme encoded by the SULT1A1 gene is involved in estrogen metabolism. Previous research has suggested that the SULT1A1 copy number is linked with the plasma estradiol (E2) concentration. Here, a total of 34 premenopausal breast cancer patients, selected from the Thai Tamoxifen (TTAM) Project, were screened for their SULT1A1 copy number, plasma E2 concentration and ADRs. The mean age was 44.3±11.1 years, and they were subtyped as ER+/ progesterone receptor (PR) + (28 patients), ER+/ PR- (5 patients) and ER-/PR- (1 patient). Three patients reported ADRs, which were irregular menstruation (2 patients) and vaginal discharge (1 patient). Most (33) patients had two SULT1A1 copies, with one patient having three copies. The median plasma E2 concentration was 1,575.6 (IQR 865.4) pg/ml. Patients with ADRs had significantly higher plasma E2 concentrations than those patients without ADRs (p = 0.014). The plasma E2 concentration was numerically higher in the patient with three SULT1A1 copies, but this lacked statistical significance.

  6. Influence of different susceptibility testing methods and media on determination of the relevant fluconazole minimum inhibitory concentrations for heavy trailing Candida isolates with low-high phenotype.

    Alp, Sehnaz; Sancak, Banu; Hascelik, Gulsen; Arikan, Sevtap


    We investigated the incidence of trailing growth with fluconazole in 101 clinical Candida isolates (49 C. albicans and 52 C. tropicalis) and tried to establish the convenient susceptibility testing method and medium for fluconazole minimum inhibitory concentration (MIC) determination. MICs were determined by CLSI M27-A2 broth microdilution (BMD) and Etest methods on RPMI-1640 agar supplemented with 2% glucose (RPG) and on Mueller-Hinton agar supplemented with 2% glucose and 0.5 μg ml(-1) methylene blue (GMB). BMD and Etest MICs were read at 24 and 48 h, and susceptibility categories were compared. All isolates were determined as susceptible with BMD, Etest-RPG and Etest-GMB at 24 h. While all isolates were interpreted as susceptible at 48 h on Etest-RPG and Etest-GMB, one C. albicans isolate was interpreted as susceptible-dose dependent (S-DD) and two C. tropicalis isolates were interpreted as resistant with BMD. On Etest-RPG, trailing growth caused widespread microcolonies within the inhibition zone and resulted in confusion in MIC determination. On Etest-GMB, because of the nearly absence of microcolonies within the zone of inhibition, MICs were evaluated more easily. We conclude that, for the determination of fluconazole MICs of trailing Candida isolates, the Etest method has an advantage over BMD and can be used along with this reference method. Moreover, GMB appears more beneficial than RPG for the fluconazole Etest. © 2009 Blackwell Verlag GmbH.

  7. Relationship between seminal plasma zinc concentration and spermatozoa-zona pellucida binding and the ZP-induced acrosome reaction in subfertile men.

    Liu, De-Yi; Sie, Boon-Shih; Liu, Ming-Li; Agresta, Franca; Baker, H W Gordon


    The aim of this study was to determine the relationship between seminal zinc concentration and spermatozoa-zona pellucida (ZP) binding and the ZP-induced acrosome reaction (ZPIAR) in subfertile men. Semen analyses and seminal zinc concentration assessments were carried out according to the World Health Organization manual for 458 subfertile men. A spermatozoa-ZP interaction test was carried out by incubating 2 x 10(6) motile spermatozoa with a group of four unfertilized oocytes obtained from a clinical in vitro fertilization programme. After 2 h of incubation, the number of spermatozoa bound per ZP and the ZPIAR of ZP-bound spermatozoa were examined. The effect of adding 0.5 mmol L(-1) zinc to the media on the ZPIAR of spermatozoa from normozoospermic men was also tested in vitro. Seminal zinc concentration positively correlated with sperm count and duration of abstinence, but negatively correlated with semen volume. On analysis of data from all participants, both spermatozoa-ZP binding and the ZPIAR were significantly correlated with sperm motility and normal morphology, but not with seminal zinc concentration. However, in men with normozoospermic semen, the seminal zinc concentration was significantly higher in men with defective ZPIAR (or= 16%) (P zinc to the culture media had no effect on spermatozoa-ZP binding, but significantly reduced the ZPIAR in vitro (P zinc concentration is correlated with sperm count and the duration of abstinence in subfertile men. In men with normozoospermic semen, high seminal zinc concentration may have an adverse effect on the ZPIAR.

  8. Stabilisation goals for concentrations of climate-relevant gaseous emissions: Effects and emission pathways. Final report; Stabilisierungsziele fuer Treibhausgaskonzentrationen: Eine Abschaetzung der Auswirkungen und der Emissionspfade. Abschlussbericht

    Onigkeit, J.; Alcamo, J.; Kaspar, F.; Roesch, T.


    Two different stabilisation goals were assumed, i.e. 550 ppm and 450 ppm of carbon dioxide. First, the global anthropogenic carbon dioxide emissions were calculated that are permissible to reach these goals. Secondly, the global and regional environmental effects of these concentration goals were assessed. In this, carbon dioxide, nitric oxides and methane emissions from power generation, industry and agriculture were considered. Apart from an investigation of the global reduction strategies required, a key was developed for sharing the global reduction loads between Annex B countries and non-Annex B countries. To reach a stable concentration of 550 ppm carbon dioxide in the atmosphere, the global anthropogenic carbon dioxide emissions per annum may increase slightly until 2030 but must be lowered to the 1990 level by 2100. In the case of 450 ppm, the 1990 level must even be halved by 2100. The consequences of climate change for agriculture, natural vegetation, availability of water, and sea levels were investigated in consideration of regional variations in carbon dioxide emissions and emission reduction measures. In spite of extensive emission control, the area of reduced agricultural productivity will grow rapidly in both cases, and natural vegetation will be endangered, although with strong regional variations. [German] Ausgehend von zwei langfristigen Klimaschutzzielen (Stabilisierung der atmosphaerischen CO{sub 2}-Konzentration bei 550 ppm und bei 450 ppm) wurde mit Hilfe des IMAGE 2.1 Modells: (1) Eine Berechnung der globalen anthropogenen Treibhausgasemissionen durchgefuehrt, die zwischen 1990 und 2100 erlaubt sind, um diese Konzentrationsziele zu erreichen. (2) Wurde eine Abschaetzung der globalen und regionalen Umweltauswirkungen durch den Klimawandel durchgefuehrt, der mit diesen Konzentrationszielen einhergeht. Bei der Analyse wurden CO{sub 2}-, N{sub 2}O- und CH{sub 4} Emissionen aus dem Energie/Industrie- und dem landwirtschaftlichen Sektor

  9. The effects of stress concentrations on reaction progress: an example from experimental growth of magnesio-aluminate spinel at corundum - periclase interfaces under uniaxial load

    Jerabek, Petr; Abart, Rainer; Rybacki, Erik; Habler, Gerlinde


    The study aims to understand the reaction progress and chemical, microstructural and textural evolution of magnesio-aluminate spinel reaction rims formed at varying experimental settings (load, temperature and experiment duration). The spinel rims were grown at the contacts between periclase and corundum at temperatures of 1250°C to 1350°C and dry atmosphere, maintained by a constant argon gas flow, under uniaxial load of 0.026 and 0.26 kN per 9 mm2 of initial contact area. Single crystals of periclase with [100] and of corundum with [0001] perpendicular to the polished reaction interface as well as polycrystalline corundum were used as starting materials. Two loading procedures, immediate application of the load before heating and loading after the desired temperature had been reached, were used. An important byproduct of our experiments stemmed from the immediate application of the load, which led to deformation twinning and fracturing of corundum. This internal deformation of corundum disturbed the reaction interface and introduced loci of concentrated stress due to opening of void spaces in between the reactant crystals. Whenever cracks formed in the initial stages of an experiment, the void space opened immediately and no spinel formed along these interface segments. In the case of deformation twinning, the decreased rim thickness indicates later opening of void spaces. This is because next to twins, the reaction interface is characterized by tight physical contact on the one side and less tight contact on the other side of the twin individual. The tight contacts are characterized by enhanced reaction progress which together with the overall positive volume change of the reaction and limits on plasticity of the studied phases led to the opening of void spaces at places characterized by less tight contacts. The thickness variations are less pronounced in our high load (0.26 kN) experiments where periclase behaves plastically and to some extent reduces the

  10. Design of a New Concentration Series for the Orthogonal Sample Design Approach and Estimation of the Number of Reactions in Chemical Systems.

    Shi, Jiajia; Liu, Yuhai; Guo, Ran; Li, Xiaopei; He, Anqi; Gao, Yunlong; Wei, Yongju; Liu, Cuige; Zhao, Ying; Xu, Yizhuang; Noda, Isao; Wu, Jinguang


    A new concentration series is proposed for the construction of a two-dimensional (2D) synchronous spectrum for orthogonal sample design analysis to probe intermolecular interaction between solutes dissolved in the same solutions. The obtained 2D synchronous spectrum possesses the following two properties: (1) cross peaks in the 2D synchronous spectra can be used to reflect intermolecular interaction reliably, since interference portions that have nothing to do with intermolecular interaction are completely removed, and (2) the two-dimensional synchronous spectrum produced can effectively avoid accidental collinearity. Hence, the correct number of nonzero eigenvalues can be obtained so that the number of chemical reactions can be estimated. In a real chemical system, noise present in one-dimensional spectra may also produce nonzero eigenvalues. To get the correct number of chemical reactions, we classified nonzero eigenvalues into significant nonzero eigenvalues and insignificant nonzero eigenvalues. Significant nonzero eigenvalues can be identified by inspecting the pattern of the corresponding eigenvector with help of the Durbin-Watson statistic. As a result, the correct number of chemical reactions can be obtained from significant nonzero eigenvalues. This approach provides a solid basis to obtain insight into subtle spectral variations caused by intermolecular interaction.

  11. Reaction rate reconstruction from biomass concentration measurement in bioreactors using modified second-order sliding mode algorithms.

    De Battista, Hernán; Picó, Jesús; Garelli, Fabricio; Navarro, José Luis


    This paper deals with the estimation of unknown signals in bioreactors using sliding observers. Particular attention is drawn to estimate the specific growth rate of microorganisms from measurement of biomass concentration. In a recent article, notions of high-order sliding modes have been used to derive a growth rate observer for batch processes. In this paper we generalize and refine these preliminary results. We develop a new observer with a different error structure to cope with other types of processes. Furthermore, we show that these observers are equivalent, under coordinate transformations and time scaling, to the classical super-twisting differentiator algorithm, thus inheriting all its distinctive features. The new observers' family achieves convergence to time-varying unknown signals in finite time, and presents the best attainable estimation error order in the presence of noise. In addition, the observers are robust to modeling and parameter uncertainties since they are based on minimal assumptions on bioprocess dynamics. In addition, they have interesting applications in fault detection and monitoring. The observers performance in batch, fed-batch and continuous bioreactors is assessed by experimental data obtained from the fermentation of Saccharomyces Cerevisiae on glucose.

  12. Adverse reactions to metal on polyethylene implants: Highly destructive lesions related to elevated concentration of cobalt and chromium in synovial fluid.

    Eltit, Felipe; Assiri, Ali; Garbuz, Donald; Duncan, Clive; Masri, Bassam; Greidanus, Nelson; Bell, Robert; Sharma, Manju; Cox, Michael; Wang, Rizhi


    Adverse local tissue reactions (ALTR) are the primary cause of failure of metal on metal (MoM) hip implants, and fewer but not negligible number cases of nonmodular metal on polyethylene (MoP) implants. In this study, we analyzed 17 cases of MoP ALTR, and equal number of MoM, by histological observation, cobalt and chromium concentration in serum and synovial fluid and cytokine analysis in ALTR tissues. ALTRs in MoP are highly necrotic, affecting larger areas than MoM ALTRs. Degenerative changes in blood vessels' wall were seen in all MoP ALTRs. The concentration of cobalt and chromium was higher in synovial fluid but lower in serum of MoP patients compared to MoM patients. Elevated concentrations of chemokines were observed in ALTR tissues. We conclude that ALTRs in MoP systems are highly necrotizing lesions that seem to have a similar development to ALTRs in MoM. Alteration of vessels wall seems to have a role in the tissues necrosis, as well as the elevated concentration of cobalt and chromium in synovial fluid of MoP patients. Chemokines may be involved in the pathogenesis of ALTR and constitute possible diagnostic targets. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 105A: 1876-1886, 2017. © 2017 Wiley Periodicals, Inc.

  13. Reações cutâneas graves adversas a drogas: aspectos relevantes ao diagnóstico e ao tratamento - Parte II Severe cutaneous adverse drug reactions: relevant aspects to diagnosis and treatment - Part II

    Paulo Ricardo Criado


    Full Text Available As reações cutâneas graves adversas à droga são as que geralmente necessitam de internação hospitalar, por vezes em unidade de terapia intensiva ou de queimados, com observação minuciosa dos sinais vitais e da função de órgãos internos. O objetivo é descrever estas reações facilitando o seu reconhecimento e tratamento. Fazem parte deste grupo a Síndrome de Hipersensibilidade à Droga (SHD, a Pustulose Exantemática Generalizada Aguda (PEGA, a Necrose Cutânea induzida por Anticoagulante, as Vasculites de Pequenos Vasos (VPV, a Vasculite de Hipersensibilidade ao Propiltiouracil (VHP e as Reações tipo Doença do Soro (RDS. A SHD tem-se tornado de elevada relevância clínica devido ao uso amplo dos anticonvulsivantes aromáticos e da dapsona, utilizada no tratamento de doenças como a acne e a hanseníase. A PEGA é determinada principalmente pelos derivados beta-lactâmicos e tem como principal diagnóstico diferencial a psoríase pustulosa generalizada. As VPV tegumentares podem refletir uma doença multissistêmica subjacente, com danos graves em órgãos nobres, como os rins, pulmões e sistema hematológico, com morbidade elevada e possível letalidade. Abordamos as características clínicas e o tratamento destas reações adversas à droga.Severe cutaneous adverse drug reactions generally require hospitalization, sometimes in intensive care or burns units, for observation of the vital signs and the visceral function. The objective was to describe these reactions in order to facilitate recognition and treatment. This group of drug reactions includes drug hypersensitivity syndrome (DHS, acute generalized exanthematous pustulosis (AGEP, anticoagulant-induced skin necrosis, small-vessel vasculitis (SVV, propylthiouracil hypersensitivity vasculitis and serum sickness disease. DHS has been most relevant due to universal prescription of aromatic anticonvulsant drugs and dapsone use in the treatment of some diseases such as acne

  14. Some Environmentally Relevant Reactions of Cerium Oxide

    Janoš Pavel


    Full Text Available Reactive forms of cerium oxide were prepared by a thermal decomposition of various precursors, namely carbonates, oxalates and citrates, commercially available nanocrystalline cerium oxide (nanoceria was involved in the study for comparison. Scanning electron microscopy (SEM and x-ray diffraction analysis (XRD were used to examine the morphology and crystallinity of the samples, respectively, whereas the Brunauer-Emmett-Teller (BET method of nitrogen adsorption was used to determine surface areas. Interactions of cerium oxide with some phosphorus-containing compounds were investigated. Some of the examined samples, especially those prepared by annealing from carbonate precursors, exhibited an outstanding ability to destroy highly toxic organophosphates, such as pesticides (parathion methyl, or nerve agents (soman, VX. There were identified some relations between the degradation efficiency of cerium oxides and their crystallinity. It was also shown that cerium oxide is able to destroy one of widely used flame retardants - triphenyl phosphate. A phosphatase-mimetic activity of various cerium oxides was examined with the aid of a standardized phosphatase test.

  15. Relevance of diffusion through bacterial spore coats/membranes and the associated concentration boundary layers in the initial lag phase of inactivation: a case study for Bacillus subtilis with ozone and monochloramine.

    Fernando, W J N; Othman, R


    Disinfectants are generally used to inactivate microorganisms in solutions. The process of inactivation involves the disinfectant in the liquid diffusing towards the bacteria sites and thereafter reacting with bacteria at rates determined by the respective reaction rates. Such processes have demonstrated an initial lag phase followed by an active depletion phase of bacteria. This paper attempts to study the importance of the combined effects of diffusion of the disinfectant through the outer membrane of the bacteria and transport through the associated concentration boundary layers (CBLs) during the initial lag phase. Mathematical equations are developed correlating the initial concentration of the disinfectant with time required for reaching a critical concentration (C*) at the inner side of the membrane of the cell based on diffusion of disinfectant through the outer membranes of the bacteria and the formation of concentration boundary layers on both sides of the membranes. Experimental data of the lag phases of inactivation already available in the literature for inactivation of Bacillus subtilis spores with ozone and monochloramine are tested with the equations. The results seem to be in good agreement with the theoretical equations indicating the importance of diffusion process across the outer cell membranes and the resulting CBL's during the lag phase of disinfection.

  16. Formaldehyde concentration in diagnostic patch testing

    Trattner, A; Johansen, J D; Menné, T


    Exposure to formaldehyde is common from both consumer products and industry. The reliability of the patch test is essential for the diagnosis of formaldehyde allergy as it is difficult to suspect from the patient's history. The recommended formaldehyde patch test concentration has been reduced over......% in consecutively patch-tested patients, with respect to frequency of positive patch test reactions, strength of patch test reactions to different formaldehyde test concentrations, irritancy and relevance. The study included 3734 consecutively patch tested patients. 121 gave a positive reaction to 1% and/or 2...... gave few additional positive cases compared to D 3/4. Problems related to relevance are discussed. Based on present knowledge, a 1% patch test concentration for formaldehyde is recommended....

  17. Modified concentration method for the detection of enteric viruses on fruits and vegetables by reverse transcriptase-polymerase chain reaction or cell culture.

    Dubois, Eric; Agier, Cécilia; Traoré, Ousmane; Hennechart, Catherine; Merle, Ghislaine; Crucière, Catherine; Laveran, Henri


    Fruits and vegetables may act as a vehicle of human enteric virus if they are irrigated with sewage-contaminated water or prepared by infected food handlers. An elution-concentration method was modified to efficiently detect, by reverse transcriptase-polymerase chain reaction (RT-PCR) or by cell culture, contamination by poliovirus, hepatitis A virus (HAV), and Norwalk-like virus (NLV) of various fresh and frozen berries and fresh vegetables. The protocol included washing the fruit or vegetable surface with 100 mM Tris-HCl, 50 mM glycine, and 3% beef extract, pH 9.5 buffer, which favors viral elution from acid-releasing berries, supplemented with 50 mM MgCl2 to reduce the decrease in viral infectivity during the process. The viral concentration method was based on polyethylene glycol precipitation. Copurified RT-PCR inhibitors and cytotoxic compounds were removed from viral concentrates by chloroform-butanol extraction. Viruses from 100 g of vegetal products could be recovered in volumes of 3 to 5 ml. Viral RNAs were isolated by a spin column method before molecular detection or concentrates were filtered (0.22-microm porosity) and inoculated on cell culture for infectious virus detection. About 15% of infectious poliovirus and 20% of infectious HAV were recovered from frozen raspberry surfaces. The percentage of viral RNA recovery was estimated by RT-PCR to be about 13% for NLV, 17% for HAV, and 45 to 100% for poliovirus. By this method, poliovirus and HAV RNA were detected on products inoculated with a titer of about 5 x 10(1) 50% tissue culture infectious dose per 100 g. NLV RNA was detected at an initial inoculum of 1.2 x 10(3) RT-PCR amplifiable units. This method would be useful for the viral analysis of fruits or vegetables during an epidemiological investigation of foodborne diseases.

  18. Evaluation of Real-Time Quantitative Polymerase Chain Reaction (qPCR) to Determine Escherichia coli Concentrations at Two Lake Erie Beaches

    Kephart, Christopher M.; Bushon, Rebecca N.


    During the recreational seasons of 2006 and 2007, the quantitative polymerase chain reaction (qPCR) method was used to determine Escherichia coli (E. coli) concentrations in samples from two Lake Erie beaches. Results from the qPCR method were compared to those obtained by traditional culturing on modified mTEC agar. Regression analysis showed strong, statistically significant correlations between results from the two methods for both years. Correlation coefficients at Edgewater and Villa Angela Beaches were 0.626 and 0.789 for 2006 and 0.667 and 0.829 for 2007, respectively. Linear regression analyses were done to determine how well E. coli concentrations could have been predicted from qPCR results. These hypothetical predictions were compared to the current practice of determining recreational water quality from E. coli concentrations determined for samples collected on the previous day. The qPCR method resulted in a greater percentage of correct predictions of water-quality exceedances than the current method for both beaches and both years. However, because regression equations differed somewhat between both sites and both years, the study did not result in any single relation reliable enough to use for actual real-time prediction of water-quality exceedances for either beach; therefore, a posterior analysis of data was done. Additional years of data may be needed to develop such a relation. Results from this study support the continued development and testing of a qPCR method for providing rapid and accurate estimates of E. coli concentrations for monitoring recreational water quality.

  19. Direct determination of atom and radical concentrations in thermal reactions of hydrocarbons and other gases. Progress report, June 1, 1976--December 31, 1976. [Design and construction of shock tube for measuring reaction products

    Skinner, G. B.; Lifshitz, A.


    A shock tube has been designed and constructed for the purpose of measuring atom and radical concentrations in thermal reactions of gases. Design features which lead to extremely low levels of contamination include a turbomolecular vacuum pump, metal O-rings in the test section, stainless steel bellows-seal valves, and provision for baking all components to 150 to 200/sup 0/C. The optical system consists of a microwave discharge lamp through which various gas mixtures may flow at low pressures, MgF/sub 2/ windows on the shock tube, and a photodetector. For initial measurements of H and O atoms, a solar blind photomultiplier sensitive at 110 to 140 nm is being used. During the balance of the contract year (January 1--May 31) testing of the shock tube will be completed, the light source will be characterized, and measurements of H atom concentrations in shock-heated mixtures of CH/sub 4/--Ar and H/sub 2/--O/sub 2/--Ar will be started.

  20. Mineral dissolution in the Cape Cod aquifer, Massachusetts, USA: I . Reaction stoichiometry and impact of accessory feldspar and glauconite on strontium isotopes, solute concentrations, and REY distribution

    Bau, Michael; Alexander, Brian; Chesley, John T.; Dulski, Peter; Brantley, Susan L.


    To compare relative reaction rates of mineral dissolution in a mineralogically simple groundwater aquifer, we studied the controls on solute concentrations, Sr isotopes, and rare earth element and yttrium (REY) systematics in the Cape Cod aquifer. This aquifer comprises mostly carbonate-free Pleistocene sediments that are about 90% quartz with minor K-feldspar, plagioclase, glauconite, and Fe-oxides. Silica concentrations and pH in the groundwater increase systematically with increasing depth, while Sr isotopic ratios decrease. No clear relationship between 87Sr/ 86Sr and Sr concentration is observed. At all depths, the 87Sr/ 86Sr ratio of the groundwater is considerably lower than the Sr isotopic ratio of the bulk sediment or its K-feldspar component, but similar to that of a plagioclase-rich accessory separate obtained from the sediment. The Si- 87Sr/ 86Sr-depth relationships are consistent with dissolution of accessory plagioclase. In addition, solutes such as Sr, Ca, and particularly K show concentration spikes superimposed on their respective general trends. The K-Sr- 87Sr/ 86Sr systematics suggests that accessory glauconite is another major solute source to Cape Cod groundwater. Although the authigenic glauconite in the Cape Cod sediment is rich in Rb, it is low in in-grown radiogenic 87Sr because of its young Pleistocene age. The low 87Sr/ 86Sr ratios are consistent with equilibration of glauconite with seawater. The impact of glauconite is inferred to vary due to its variable abundance in the sediments. In the Cape Cod groundwater, the variation of REY concentrations with sampling depth resembles that of K and Rb, but differs from that of Ca and Sr. Shale-normalized REY patterns are light REY depleted, show negative Ce anomalies and super-chondritic Y/Ho ratios, but no Eu anomalies. REY input from feldspar, therefore, is insignificant compared to input from a K-Rb-bearing phase, inferred to be glauconite. These results emphasize that interpretation of

  1. Nutritionally relevant concentrations of resveratrol and hydroxytyrosol mitigate oxidative burst of human granulocytes and monocytes and the production of pro-inflammatory mediators in LPS-stimulated RAW 264.7 macrophages.

    Bigagli, Elisabetta; Cinci, Lorenzo; Paccosi, Sara; Parenti, Astrid; D'Ambrosio, Mario; Luceri, Cristina


    The health benefits of bio-active phenolic compounds have been largely investigated in vitro at concentrations which exceed those reachable in vivo. We investigated and compared the anti-inflammatory effects of resveratrol, hydroxytyrosol and oleuropein at physiologically relevant concentrations by using in vitro models of inflammation. Human granulocytes and monocytes were stimulated with phorbol myristate acetate (PMA) and the ability of resveratrol, hydroxytyrosol and oleuropein to inhibit the oxidative burst and CD11b expression was measured. Nitric oxide (NO), prostaglandin E2 (PGE2) levels, COX-2, iNOS, TNFα, IL-1β and miR-146a expression and activation of the transcription factor Nrf2 were evaluated in macrophages RAW 264.7 stimulated with LPS (1μg/ml) for 18h, exposed to resveratrol, hydroxytyrosol and oleuropein (5 and 10μM). Synergistic effects were explored as well, together with the levels of PGE2, COX-2 and IL-1β expression in macrophages after 6h of LPS stimulation. PGE2 and COX-2 expression were also assessed on human monocytes. All the tested compounds inhibited granulocytes oxidative burst in a concentration dependent manner and CD11b expression was also significantly counteracted by resveratrol and hydroxytyrosol. The measurement of oxidative burst in human monocytes produced similar effects being resveratrol more active. Hydroxytyrosol and resveratrol inhibited the production of NO and PGE2 but did not reduce iNOS, TNFα or IL-1β gene expression in LPS-stimulated RAW 264.7 for 18h. Resveratrol slightly decreased COX-2 expression after 18h but not after 6h, but reduced PGE2 levels after 6h. Resveratrol and hydroxytyrosol 10μM induced NRf2 nuclear translocation and reduced miR-146a expression in LPS treated RAW 264.7. Overall, we reported an anti-inflammatory effect of resveratrol and hydroxytyrosol at low, nutritionally relevant concentrations, involving the inhibition of granulocytes and monocytes activation, the modulation of miR-146a

  2. A New General Method for Simultaneous Fitting of Temperature- and Concentration-Dependence of Reaction Rates Yields Kinetic and Thermodynamic Parameters for HIV Reverse Transcriptase Specificity.

    Li, An; Ziehr, Jessica L; Johnson, Kenneth A


    Recent studies have demonstrated the dominant role of induced-fit in enzyme specificity of HIV reverse transcriptase and many other enzymes. However, relevant thermodynamic parameters are lacking and equilibrium thermodynamic methods are of no avail because the key parameters can only determined by kinetic measurement. By modifying KinTek Explorer software, we present a new general method for globally fitting data collected over a range of substrate concentrations and temperatures and apply it to HIV reverse transcriptase. Fluorescence stopped-flow methods were used to record the kinetics of enzyme conformational changes that monitor nucleotide binding and incorporation. The nucleotide concentration dependence was measured at temperatures ranging from 5 to 37C and the raw data were fit globally to derive a single set of rate constants at 37C and a set of activation enthalpy terms to account for the kinetics at all other temperatures. This comprehensive analysis afforded thermodynamic parameters for nucleotide binding (Kd, ΔG, ΔH, ΔS at 37C), and kinetic parameters for enzyme conformational changes and chemistry (rate constants and activation enthalpy). Comparisons between wild-type enzyme and a mutant resistant to nucleoside analogs used to treat HIV infections reveal that the ground state binding is weaker and the activation enthalpy for the conformational change step is significantly larger for the mutant. Further studies to explore the structural underpinnings of the observed thermodynamics and kinetics of the conformational change step may help to design better analogs to treat HIV infections and other diseases. Our new method is generally applicable to enzyme and chemical kinetics.

  3. Clinically relevant concentration of pregabalin has no acute inhibitory effect on excitation of dorsal horn neurons under normal or neuropathic pain conditions: An intracellular calcium-imaging study in spinal cord slices from adult rats.

    Baba, Hiroshi; Petrenko, Andrey B; Fujiwara, Naoshi


    Pregabalin is thought to exert its therapeutic effect in neuropathic pain via binding to α2δ-1 subunits of voltage-gated calcium (Ca(2+)) channels. However, the exact analgesic mechanism after its binding to α2δ-1 subunits remains largely unknown. Whether a clinical concentration of pregabalin (≈10μM) can cause acute inhibition of dorsal horn neurons in the spinal cord is controversial. To address this issue, we undertook intracellular Ca(2+)-imaging studies using spinal cord slices with an intact attached L5 dorsal root, and examined if pregabalin acutely inhibits the primary afferent stimulation-evoked excitation of dorsal horn neurons in normal rats and in rats with streptozotocin-induced painful diabetic neuropathy. Under normal conditions, stimulation of a dorsal root evoked Ca(2+) signals predominantly in the superficial dorsal horn. Clinically relevant (10μM) and a very high concentration of pregabalin (100μM) did not affect the intensity or spread of dorsal root stimulation-evoked Ca(2+) signals, whereas an extremely high dose of pregabalin (300μM) slightly but significantly attenuated Ca(2+) signals in normal rats and in diabetic neuropathic (DN) rats. There was no difference between normal rats and DN rats with regard to the extent of signal attenuation at all concentrations tested. These results suggest that the activity of dorsal horn neurons in the spinal cord is not inhibited acutely by clinical doses of pregabalin under normal or DN conditions. It is very unlikely that an acute inhibitory action in the dorsal horn is the main analgesic mechanism of pregabalin in neuropathic pain states. Copyright © 2016 Elsevier B.V. All rights reserved.

  4. On the impedance of galvanic cells XXVII. The temperature-dependence of the kinetic parameters of the hydrogen electrode reaction on mercury in concentrated HI

    Dekker, B.G.; Sluyters-Rehbach, M.; Sluyters, J.H.


    The impedance of a dropping mercury electrode in 57% HI (7.6 M) was measured at temperatures between −35° and +25°C. In a certain potential and temperature region, two reactions were found to be proceeding simultaneously: the reversible Hg/HgI4−2 reaction and the irreversible H+/H2(Hg) reaction. Ana

  5. Up-regulation of visfatin expression in subjects with hyperthyroidism and hypothyroidism is partially relevant to a nonlinear regulation mechanism between visfatin and tri-iodothyronine with various concentrations

    HAN Jing; ZHANG Tian-ou; XIAO Wen-hua; CHANG Cui-qing; AI Hua


    Background Visfatin,a visceral fat-derived adipocytokine,plays a significant physiological function in lipid metabolism.However,the precise function of visfatin and its regulation by thyroid hormones are still unknown.This study observed the plasma visfatin concentrations in subjects with hyperthyroidism and hypothyroidism in vivo,and investigated the possible regulation mechanism between visfatin and tri-iodothyronine (T3) in vitro as a further interpretation.Methods The experiment in vivo included clinical subjects (57 patients with thyroid dysfunction and 29 euthyroid healthy volunteers) and an animal model (24 Wistar rats).All subjects were divided into hyperthyroidism,hypothyroidism and euthyroidism groups,with plasma thyroid hormones,thyrotropin,visfatin and triglyceride concentrations determined.Visfatin mRNA expression in visceral fat and liver of rats was detected by quantitative real-time reverse transcription-polymerase chain reaction (RT-PCR).The experiment in vitro studied 3T3-L1 cells and visfatin mRNA expression under nine different T3concentrations (0,0.1,0.25,0.5,1,5,10,20,100 nmol/L) using quantitative real-time RT-PCR.Results Clinical subjects and animal models showed elevated plasma visfatin concentrations in the hyperthyroidism group (20.466 ng/ml (15.263,26.795 ng/ml) and (1209.164±165.292) ng/L) and hypothyroidism group (12.457 ng/ml (11.115,15.454 ng/ml) and (1205.425±109.200) ng/L) compared to euthyroidism group (6.891 ng/ml (5.888,8.803 ng/ml) and (926.650±54.002) ng/L,P <0.001).For animal models,visfatin mRNA expression in visceral fat in the hyperthyroidism and hypothyroidism groups increased about 3.33-fold and 1.98-fold compared to the euthyroidism group (P <0.001),which was positively correlated with plasma visfatin concentrations (r=0.713,P <0.001).However,no significant group difference (P >0.05) and correlation (r=0.121,P=0.572) was found in the liver.T3 induced a remarkable increase of visfatin mRNA expression in 3T3-L1

  6. A sensitive and a rapid multiplex polymerase chain reaction for the identification of Candida species in concentrated oral rinse specimens in patients with diabetes.

    Sampath, Asanga; Weerasekera, Manjula; Gunasekara, Chinthika; Dilhari, Ayomi; Bulugahapitiya, Uditha; Fernando, Neluka


    Oral candidiasis is being frequently recognized in patients with diabetes, and is associated with multiple pathogens including Candida albicans, Candida parapsilosis, Candida glabrata and Candida tropicalis. The aim of this study was to evaluate a usefulness of a Multiplex Polymerase Chain Reaction as a rapid diagnostic tool for identification of four oral Candida pathogens in patients with diabetes. A multiplex PCR was optimized to identify four Candida species in concentrated oral rinse samples. Common reverse primer, ITS4 and four species-specific forward primers targeting ITS1 and ITS2 regions of yeast genome were used. Species-specific single amplicon were detected by agarose gel electrophoresis. Performance efficacy of multiplex PCR was compared with phenotypic identification. Out of 100 oral rinse samples, 72 were culture positive and of these 43 were at risk of oral Candida infection (>600cfu/ml). Multiple Candida species including C. albicans, C. parapsilosis and C. tropicalis were identified in 22 samples which had risk of oral Candida infection. In total, 85 patients were positive for Candida by multiplex PCR and of them 49 had multiple Candida species. All 43 colonized specimens were also positive by multiplex PCR. C. albicans was the most predominant organism (75/85) followed by C. parapsilosis (47/85), C. tropicalis (17/85) and C. glabrata (6/85). In specimens with multiple species, the two most common organisms were C. albicans and C. parapsilosis. Multiplex PCR yielded a sensitivity of 10 Candida cells/ml of oral rinse sample. Multiplex PCR is found to be rapid, sensitive and specific than phenotypic identification methods in discriminating multiple Candida species in oral rinse specimens.

  7. Sensitivity of multiplex real-time PCR reactions, using the LightCycler and the ABI PRISM 7700 Sequence Detection System, is dependent on the concentration of the DNA polymerase.

    Exner, M M; Lewinski, M A


    The introduction of multiplex PCR techniques to clinical laboratories has provided a means to streamline assays and to produce multiple results with minimal effort. While this methodology is very beneficial, care must be taken to ensure that reactions are properly optimized to allow for maximum sensitivity. This study was conducted to determine whether the sensitivity of multiplex-real-time PCR assays could be improved by increasing the concentration of DNA polymerase within a reaction. Multiplex reactions were designed to simultaneously detect the human HLA-DQ gene and a sequence from the UL83 region of the CMV genome. Two real-time PCR systems, one utilizing AmpliTaq Gold DNA polymerase and the ABI 7700 Sequence Detection System, and one utilizing FastStart Taq DNA polymerase and the Roche LightCycler were tested. The results indicated that increasing the AmpliTaq Gold concentration from 0.050 to 0.10 U/microl and the FastStart Taq concentration from 0.1875 to 0.375 U/microl increased detection sensitivity from 5,000 to 50 CMV copies per PCR reaction. In separate experiments, commercially prepared mastermixes were utilized for both real-time PCR platforms as per the manufacturer's suggestions or with the addition of supplemental DNA polymerase. In assays designed to detect 4 CMV genome copies per reaction, the addition of 2.5 U of AmpliTaq Gold to TaqMan Universal Mastermix increased the detection rate from 21 to 67%, and the addition of 5 U of FastStart Taq to FastStart DNA Master Hybridization Probes mastermix increased the detection rate from 17 to 56%. These results indicate that increasing the DNA polymerase concentration in multiplex real-time PCR reactions may be a simple way to optimize assay sensitivity.

  8. Study of turbulent jet diffusion with competitive-consecutive reaction. 2nd Report. Properties of reactive concentration field; Renzoku kyoso hanno wo tomonau ranryu funryu kakusan no kenkyu. 2. Hanno nodoba no tokusei

    Kubo, T.; Sakai, Y.; Nakamura, I. [Nagoya University, Nagoya (Japan); Ota, I.


    The diffusion field with a competitive-consecutive reaction (A + B {yields} R, R + B {yields} S) in a turbulent liquid jet has been experimentally investigated. The water solution of species Band non-reactive dye Y is issued into the main flow including species A. The instantaneous concentrations of two reactive species (R and S) and a non-reactive dye (Y) were measured simultaneously by the light absorption spectrometric method. The instantaneous concentrations of species A and B were determined by the conserved scalar theory. Since the reaction rate constant of the primary reaction is much larger than that of the secondary reaction, the species R starts to he produced efficiently from the neighborhood of the nozzle exit, while the species S is mainly produced in the downstream region. The skewness of the concentration PDF of reactants A and B on the jet axis show the positive values in the downstream region, while those of products R and S show the negative values. (author)

  9. Microfluidic chemical reaction circuits

    Lee, Chung-cheng; Sui, Guodong; Elizarov, Arkadij; Kolb, Hartmuth C.; Huang, Jiang; Heath, James R.; Phelps, Michael E.; Quake, Stephen R.; Tseng, Hsian-rong; Wyatt, Paul; Daridon, Antoine


    New microfluidic devices, useful for carrying out chemical reactions, are provided. The devices are adapted for on-chip solvent exchange, chemical processes requiring multiple chemical reactions, and rapid concentration of reagents.

  10. Kinetic analysis of γ-glutamyltransferase reaction process for measuring activity via an integration strategy at low concentrations of γ-glutamyl p-nitroaniline

    Zhi-rong LI; Yin LIU; Xiao-lan YANG; Jun PU; Bei-zhong LIU; Yong-hua YUAN; Yan-ling XIE; Fei LIAO


    At 0.12 mmol/L γ-glutamyl p-nitroaniline (GGPNA), an improved integrated method was developed for kinetic analysis of γ-glutamyltransferase (GGT) reaction process and the integration with the classical initial rate method to measure serum GGT. For the improved integrated method, an integrated rate equation, which used the predictor variable of reaction time and considered inhibitions by both GGPNA and products, was nonlinearly fit to GGT reaction processes. For the integration strategy, classical initial rates were estimated when GGPNA consumption percentages were below 50%; otherwise, maximal reaction rates of GGT were estimated by the improved integrated method and converted into initial rates according to the differential rate equation at 0.11 mmol/L GGPNA. The integration strategy was validated using optimized GGT kinetic parameters and 10-s intervals to record reaction curves within 8.0 min. By the integration strategy, there was a linear response from 0.9 to 32.0 U/L GGT, coefficients of variation were below 3.5% for GGT from 8.0 to 32.0 U/L (n=5), and GGT activities in clinical sera responded linearly to their classical initial rates at 2.00 mmol/L GGPNA with an expected slope. Therefore, the integration strategy was successful in measuring GGT at 0.12 mmol/L GGPNA.

  11. Why relevance theory is relevant for lexicography

    Bothma, Theo; Tarp, Sven


    , socio-cognitive and affective relevance. It then shows, at the hand of examples, why relevance is important from a user perspective in the extra-lexicographical pre- and post-consultation phases and in the intra-lexicographical consultation phase. It defines an additional type of subjective relevance...... that is very important for lexicography as well as for information science, viz. functional relevance. Since all lexicographic work is ultimately aimed at satisfying users’ information needs, the article then discusses why the lexicographer should take note of all these types of relevance when planning a new...... dictionary project, identifying new tasks and responsibilities of the modern lexicographer. The article furthermore discusses how relevance theory impacts on teaching dictionary culture and reference skills. By integrating insights from lexicography and information science, the article contributes to new...

  12. X-ray Spectroscopic Characterization of Co(IV) and Metal-Metal Interactions in Co4O4: Electronic Structure Contributions to the Formation of High-Valent States Relevant to the Oxygen Evolution Reaction.

    Hadt, Ryan G; Hayes, Dugan; Brodsky, Casey N; Ullman, Andrew M; Casa, Diego M; Upton, Mary H; Nocera, Daniel G; Chen, Lin X


    The formation of high-valent states is a key factor in making highly active transition-metal-based catalysts of the oxygen evolution reaction (OER). These high oxidation states will be strongly influenced by the local geometric and electronic structures of the metal ion, which are difficult to study due to spectroscopically active and complex backgrounds, short lifetimes, and limited concentrations. Here, we use a wide range of complementary X-ray spectroscopies coupled to DFT calculations to study Co(III)4O4 cubanes and their first oxidized derivatives, which provide insight into the high-valent Co(IV) centers responsible for the activity of molecular and heterogeneous OER catalysts. The combination of X-ray absorption and 1s3p resonant inelastic X-ray scattering (Kβ RIXS) allows Co(IV) to be isolated and studied against a spectroscopically active Co(III) background. Co K- and L-edge X-ray absorption data allow for a detailed characterization of the 3d-manifold of effectively localized Co(IV) centers and provide a direct handle on the t2g-based redox-active molecular orbital. Kβ RIXS is also shown to provide a powerful probe of Co(IV), and specific spectral features are sensitive to the degree of oxo-mediated metal-metal coupling across Co4O4. Guided by the data, calculations show that electron-hole delocalization can actually oppose Co(IV) formation. Computational extension of Co4O4 to CoM3O4 structures (M = redox-inactive metal) defines electronic structure contributions to Co(IV) formation. Redox activity is shown to be linearly related to covalency, and M(III) oxo inductive effects on Co(IV) oxo bonding can tune the covalency of high-valent sites over a large range and thereby tune E(0) over hundreds of millivolts. Additionally, redox-inactive metal substitution can also switch the ground state and modify metal-metal and antibonding interactions across the cluster.

  13. Experimental investigation on moving chemical reaction boundary theory for weak-acid-strong-base system with background electrolyte KCl in large concentration.

    Cao, C X; Zhou, S L; Qian, Y A; He, Y Z; Yang, L; Qu, Q S; Chen, W K


    In this report, the moving chemical reaction boundary (MCRB) was formed with the weak acid of acetic acid (HAc) and the strong alkali of NaOH, coupled with the excess of background electrolyte KCl. The experiments were compared with the predictions by the moving chemical reaction boundary equation (MCRBE). It is very interesting that (1) the experimental results are in good agreement with the predictions with the original MCRBE if the MCRB is an anodic moving boundary, (2) however, the experiments are extremely far away from the predictions with the original MCRBE if a cathodic moving boundary. Hence, the original MCRBE must be corrected under the later situation of cathodic moving MCRB. The corrected MCRBE was well quantitatively proved to be valid for the cathodic moving MNRB formed with the same electrolytes of HAc, NaOH and KCl.

  14. Effect of odd hydrogen on ozone depletion by chlorine reactions

    Donahue, T. M.; Cicerone, R. J.; Liu, S. C.; Chameides, W. L.


    The present paper discusses how the shape of the ozone layer changes under the influence of injected ClX for several choices of two key HOx reaction rates. The two HOx reactions are: OH + HO2 yields H2O + O2 and O + HO2 yields OH + O2. Results of calculations are presented which show that the two reaction rates determine the stratospheric concentrations of OH and HO2, and that these concentrations regulate the amount by which the stratospheric ozone column can be reduced due to injections of odd chlorine. It is concluded that the amount of ozone reduction by a given mixing ratio of ClX will remain very uncertain until the significance of several possible feedback effects involving HOx in a chlorine-polluted atmosphere are determined and measurements of the reaction rates and HOx concentrations are made at the relevant temperatures.

  15. A VUV Photoionization Study of the Combustion-Relevant Reaction of the Phenyl Radical (C6H5) with Propylene (C3H6) in a High Temperature Chemical Reactor

    University of Hawaii at Manoa; Sandia National Laboratories; Zhang, Fangtong; Kaiser, Ralf I.; Golan, Amir; Ahmed, Musahid; Hansen, Nils


    We studied the reaction of phenyl radicals (C6H5) with propylene (C3H6) exploiting a high temperature chemical reactor under combustion-like conditions (300 Torr, 1,200-1,500 K). The reaction products were probed in a supersonic beam by utilizing tunable vacuum ultraviolet (VUV) radiation from the Advanced Light Source and recording the photoionization efficiency (PIE) curves at mass-to-charge ratios of m/z = 118 (C9H10+) and m/z = 104 (C8H8+). Our results suggest that the methyl and atomic hydrogen losses are the two major reaction pathways with branching ratios of 86 10 percent and 14 10 percent. The isomer distributions were probed by fitting the recorded PIE curves with a linear combination of the PIE curves of the individual C9H10 and C8H8 isomers. Styrene (C6H5C2H3) was found to be the exclusive product contributing to m/z = 104 (C8H8+), whereas 3-phenylpropene, cis-1-phenylpropene, and 2-phenylpropene with branching ratios of 96 4 percent, 3 3 percent, and 1 1 percent could account for signal at m/z = 118 (C9H10+). Although searched for carefully, no evidence of the bicyclic indane molecule could be provided. The reaction mechanisms and branching ratios are explained in terms of electronic structure calculations nicely agreeing with a recent crossed molecular beam study on this system.

  16. A VUV photoionization study of the combustion-relevant reaction of the phenyl radical (C6H5) with propylene (C3H6) in a high temperature chemical reactor.

    Zhang, Fangtong; Kaiser, Ralf I; Golan, Amir; Ahmed, Musahid; Hansen, Nils


    We studied the reaction of phenyl radicals (C(6)H(5)) with propylene (C(3)H(6)) exploiting a high temperature chemical reactor under combustion-like conditions (300 Torr, 1200-1500 K). The reaction products were probed in a supersonic beam by utilizing tunable vacuum ultraviolet (VUV) radiation from the Advanced Light Source and recording the photoionization efficiency (PIE) curves at mass-to-charge ratios of m/z = 118 (C(9)H(10)(+)) and m/z = 104 (C(8)H(8)(+)). Our results suggest that the methyl and atomic hydrogen losses are the two major reaction pathways with branching ratios of 86 ± 10% and 14 ± 10%. The isomer distributions were probed by fitting the recorded PIE curves with a linear combination of the PIE curves of the individual C(9)H(10) and C(8)H(8) isomers. Styrene (C(6)H(5)C(2)H(3)) was found to be the exclusive product contributing to m/z = 104 (C(8)H(8)(+)), whereas 3-phenylpropene, cis-1-phenylpropene, and 2-phenylpropene with branching ratios of 96 ± 4%, 3 ± 3%, and 1 ± 1% could account for the signal at m/z = 118 (C(9)H(10)(+)). Although searched for carefully, no evidence of the bicyclic indane molecule could be provided. The reaction mechanisms and branching ratios are explained in terms of electronic structure calculations nicely agreeing with a recent crossed molecular beam study on this system.

  17. Validation of the concentration profiles obtained from the near infrared/multivariate curve resolution monitoring of reactions of epoxy resins using high performance liquid chromatography as a reference method.

    Garrido, M; Larrechi, M S; Rius, F X


    This paper reports the validation of the results obtained by combining near infrared spectroscopy and multivariate curve resolution-alternating least squares (MCR-ALS) and using high performance liquid chromatography as a reference method, for the model reaction of phenylglycidylether (PGE) and aniline. The results are obtained as concentration profiles over the reaction time. The trueness of the proposed method has been evaluated in terms of lack of bias. The joint test for the intercept and the slope showed that there were no significant differences between the profiles calculated spectroscopically and the ones obtained experimentally by means of the chromatographic reference method at an overall level of confidence of 5%. The uncertainty of the results was estimated by using information derived from the process of assessment of trueness. Such operational aspects as the cost and availability of instrumentation and the length and cost of the analysis were evaluated. The method proposed is a good way of monitoring the reactions of epoxy resins, and it adequately shows how the species concentration varies over time.

  18. Effects of low concentrations of O2 and CO on the ion-clustering reactions in the lower ionosphere of Mars

    Sieck, L. W.; Gorden, R., Jr.; Ausloos, P.


    It is demonstrated that under conditions which approximate those of the Martian ionosphere traces of CO and O2 can be effectively incorporated in ion clusters via ion-molecule reaction schemes initiated by the CO2(+) ion. For example, when 0.3% CO is added to CO2, (CO)2(+), and /(CO)2CO2/(+) appear as the major cations (584 A radiation, 300 K). In mixtures containing O2 in addition to CO, (CO2,O2+) and /(CO2)2O2/(+) are important species. A recently proposed mechanism to account for the low abundance of CO and O2 in the Martian atmosphere is discussed in the light of these observations.

  19. Exposure-Relevant Ozone Chemistry in Occupied Spaces

    Coleman, Beverly Kaye [Univ. of California, Berkeley, CA (United States)


    Ozone, an ambient pollutant, is transformed into other airborne pollutants in the indoor environment. In this dissertation, the type and amount of byproducts that result from ozone reactions with common indoor surfaces, surface residues, and vapors were determined, pollutant concentrations were related to occupant exposure, and frameworks were developed to predict byproduct concentrations under various indoor conditions. In Chapter 2, an analysis is presented of secondary organic aerosol formation from the reaction of ozone with gas-phase, terpene-containing consumer products in small chamber experiments under conditions relevant for residential and commercial buildings. The full particle size distribution was continuously monitored, and ultrafine and fine particle concentrations were in the range of 10 to>300 mu g m-3. Particle nucleation and growth dynamics were characterized.Chapter 3 presents an investigation of ozone reactions with aircraft cabin surfaces including carpet, seat fabric, plastics, and laundered and worn clothing fabric. Small chamber experiments were used to determine ozone deposition velocities, ozone reaction probabilities, byproduct emission rates, and byproduct yields for each surface category. The most commonly detected byproducts included C1?C10 saturated aldehydes and skin oil oxidation products. For all materials, emission rates were higher with ozone than without. Experimental results were used to predict byproduct exposure in the cabin and compare to other environments. Byproduct levels are predicted to be similar to ozone levels in the cabin, which have been found to be tens to low hundreds of ppb in the absence of an ozone converter. In Chapter 4, a model is presented that predicts ozone uptake by and byproduct emission from residual chemicals on surfaces. The effects of input parameters (residue surface concentration, ozone concentration, reactivity of the residue and the surface, near-surface airflow conditions, and

  20. Adelmidrol increases the endogenous concentrations of palmitoylethanolamide in canine keratinocytes and down-regulates an inflammatory reaction in an in vitro model of contact allergic dermatitis.

    Petrosino, S; Puigdemont, A; Della Valle, M F; Fusco, M; Verde, R; Allarà, M; Aveta, T; Orlando, P; Di Marzo, V


    This study aimed to investigate potential new target(s)/mechanism(s) for the palmitoylethanolamide (PEA) analogue, adelmidrol, and its role in an in vitro model of contact allergic dermatitis. Freshly isolated canine keratinocytes, human keratinocyte (HaCaT) cells and human embryonic kidney (HEK)-293 cells, wild-type or transfected with cDNA encoding for N-acylethanolamine-hydrolysing acid amidase (NAAA), were treated with adelmidrol or azelaic acid, and the concentrations of endocannabinoids (anandamide and 2-arachidonoylglycerol) and related mediators (PEA and oleoylethanolamide) were measured. The mRNA expression of PEA catabolic enzymes (NAAA and fatty acid amide hydrolase, FAAH), and biosynthetic enzymes (N-acyl phosphatidylethanolamine-specific phospholipase D, NAPE-PLD) and glycerophosphodiester phosphodiesterase 1, was also measured. Brain or HEK-293 cell membrane fractions were used to assess the ability of adelmidrol to inhibit FAAH and NAAA activity, respectively. HaCaT cells were stimulated with polyinosinic-polycytidylic acid and the release of the pro-inflammatory chemokine, monocyte chemotactic protein-2 (MCP-2), was measured in the presence of adelmidrol. Adelmidrol increased PEA concentrations in canine keratinocytes and in the other cellular systems studied. It did not inhibit the activity of PEA catabolic enzymes, although it reduced their mRNA expression in some cell types. Adelmidrol modulated the expression of PEA biosynthetic enzyme, NAPE-PLD, in HaCaT cells, and inhibited the release of the pro-inflammatory chemokine MCP-2 from stimulated HaCaT cells. This study demonstrates for the first time an 'entourage effect' of adelmidrol on PEA concentrations in keratinocytes and suggests that this effect might mediate, at least in part, the anti-inflammatory effects of this compound in veterinary practice.

  1. Deep learning relevance

    Lioma, Christina; Larsen, Birger; Petersen, Casper


    train a Recurrent Neural Network (RNN) on existing relevant information to that query. We then use the RNN to "deep learn" a single, synthetic, and we assume, relevant document for that query. We design a crowdsourcing experiment to assess how relevant the "deep learned" document is, compared......What if Information Retrieval (IR) systems did not just retrieve relevant information that is stored in their indices, but could also "understand" it and synthesise it into a single document? We present a preliminary study that makes a first step towards answering this question. Given a query, we...... to existing relevant documents. Users are shown a query and four wordclouds (of three existing relevant documents and our deep learned synthetic document). The synthetic document is ranked on average most relevant of all....

  2. Effects of Low to Intermediate Water Concentrations on Proton-Coupled Electron Transfer (PCET) Reactions of Flavins in Aprotic Solvents and a Comparison with the PCET Reactions of Quinones.

    Tan, Serena L J; Novianti, Maria L; Webster, Richard D


    The electrochemical reduction mechanisms of 2 synthesized flavins (Flox) were examined in detail in deoxygenated solutions of DMSO containing varying amounts of water, utilizing variable scan rate cyclic voltammetry (ν = 0.1-20 V s(-1)), controlled-potential bulk electrolysis, and UV-vis spectroscopy. Flavin 1, which contains a hydrogen atom at N(3), is capable of donating its proton to other reduced flavin species. After 1e(-) reduction, the initially formed Fl(•-) receives a proton from another Flox to form FlH(•) (and concomitantly produce the deprotonated flavin, Fl(-)), although the equilibrium constant for this process favors the back reaction. Any FlH(•) formed at the electrode surface immediately undergoes another 1e(-) reduction to form FlH(-), which reacts with Fl(-) to form 2 molecules of Fl(•-). Further 1e(-) reduction of Fl(•-) at more negative potentials produces the dianion, Fl(2-), which can also be protonated by another Flox to form FlH(-) and Fl(-). Flavin 2, which is methylated at N(3) (and therefore has no acidic proton), undergoes a simple chemically reversible 1e(-) reduction process in DMSO provided the water content is low (solvents results in protonation of the anion radical species, Fl(•-), for both flavins, causing an increase in the amount of FlH(-) in solution. This behavior contrasts with what is observed for quinones, which are also reduced in two 1e(-) steps in aprotic organic solvents to form the radical anions and dianions, but are able to exist in hydrogen-bonded forms (with trace or added water) without undergoing protonation.

  3. Design of Low Pt Concentration Electrocatalyst Surfaces with High Oxygen Reduction Reaction Activity Promoted by Formation of a Heterogeneous Interface between Pt and CeO(x) Nanowire.

    Chauhan, Shipra; Mori, Toshiyuki; Masuda, Takuya; Ueda, Shigenori; Richards, Gary J; Hill, Jonathan P; Ariga, Katsuhiko; Isaka, Noriko; Auchterlonie, Graeme; Drennan, John


    Pt-CeO(x) nanowire (NW)/C electrocatalysts for the improvement of oxygen reduction reaction (ORR) activity on Pt were prepared by a combined process involving precipitation and coimpregnation. A low, 5 wt % Pt-loaded CeO(x) NW/C electrocatalyst, pretreated by an optimized electrochemical conditioning process, exhibited high ORR activity over a commercially available 20 wt % Pt/C electrocatalyst although the ORR activity observed for a 5 wt % Pt-loaded CeO(x) nanoparticle (NP)/C was similar to that of 20 wt % Pt/C. To investigate the role of a CeO(x) NW promotor on the enhancement of ORR activity on Pt, the Pt-CeO(x) NW interface was characterized by using hard X-ray photoelectron spectroscopy (HXPS), transmission electron microscopy (TEM), and electron energy loss spectroscopy (EELS). Microanalytical data obtained by these methods were discussed in relation to atomistic simulation performed on the interface structures. The combined techniques of HXPS, TEM-EELS, and atomistic simulation indicate that the Pt-CeO(x) NW interface in the electrocatalyst contains two different defect clusters: Frenkel defect clusters (i.e., 2Pt(i)(••) - 4O(i)″ - 4V(o)(••) - V(Ce)″″) formed in the surface around the Pt-CeO(x) NW interface and Schottky defect clusters (i.e., (Pt(Ce)″ - 2V(O)(••) - 2Ce(Ce)') and (Pt(Ce)″ - V(O)(••))) which appear in the bulk of the Pt-CeO(x) NW interface similarly to Pt-CeO(x) NP/C. It is concluded that the formation of both Frenkel defect clusters and Schottky defect clusters at the Pt-CeO(x) NW heterointerface contributes to the promotion of ORR activity and permits the use of lower Pt-loadings in these electrocatalysts.

  4. Fuzziness and Relevance Theory

    Grace Qiao Zhang


    This paper investigates how the phenomenon of fuzzy language, such as `many' in `Mary has many friends', can be explained by Relevance Theory. It is concluded that fuzzy language use conforms with optimal relevance in that it can achieve the greatest positive effect with the least processing effort. It is the communicators themselves who decide whether or not optimal relevance is achieved, rather than the language form (fuzzy or non-fuzzy) used. People can skillfully adjust the deployment of different language forms or choose appropriate interpretations to suit different situations and communication needs. However, there are two challenges to RT: a. to extend its theory from individual relevance to group relevance; b. to embrace cultural considerations (because when relevance principles and cultural protocols are in conflict, the latter tends to prevail).

  5. Perceptions of document relevance

    Peter eBruza


    Full Text Available This article presents a study of how humans perceive the relevance of documents.Humans are adept at making reasonably robust and quick decisions about what information is relevant to them, despite the ever increasing complexity and volume of their surrounding information environment. The literature on document relevance has identified various dimensions of relevance (e.g., topicality, novelty, etc., however little is understood about how these dimensions may interact.We performed a crowdsourced study of how human subjects judge two relevance dimensions in relation to document snippets retrieved from an internet search engine.The order of the judgement was controlled.For those judgements exhibiting an order effect, a q-test was performed to determine whether the order effects can be explained by a quantum decision model based on incompatible decision perspectives.Some evidence of incompatibility was found which suggests incompatible decision perspectives is appropriate for explaining interacting dimensions of relevance.

  6. Heavy metal accumulation in some aquatic insects (Coleoptera: Hydrophilidae) and tissues of Chondrostoma regium (Heckel, 1843) relevant to their concentration in water and sediments from Karasu River, Erzurum, Turkey.

    Aydoğan, Zeynep; Şişman, Turgay; İncekara, Ümit; Gürol, Ali


    The objectives of this research were to determine and compare the heavy element concentrations in two study areas in Erzurum, Turkey (Aşkale and Dumlu sites). Assessment of some heavy elements in sediment, water, fish (Chondrostoma regium) tissues, and some aquatic insects (Coleoptera: Hydrophilidae) were carried out in June to August 2014. Heavy element levels in aquatic insect samples and their associated water and sediment were analyzed by energy dispersive X-ray fluorescence (EDXRF) spectrometer. Fish tissues, from the same habitat, were measured by inductively coupled plasma mass spectrometry (ICP-MS). Eleven elements (Al, Cr, Mn, Fe, Ni, Cu, Zn, As, Cd, Hg, Pb) were measured in fish tissues, and 14 elements (Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Sr, Br, Pb) were measured in insects. According to the results, it can be said that insects were contaminated by water and sediment, thus accumulated higher concentration of some elements than their environment. The fish, which was caught from Aşkale station, accumulates significantly higher level of heavy metals than Dumlu station's fish. The results were compared with national and international standards. The values of some heavy elements were found at higher concentration than the acceptable limits. The possible consequences of these results are briefly discussed from the point of potential hazards to ecology and human health. Element concentrations in fish tissue are below the limits, which are proposed by Turkish Food Codex, FAO/WHO, and EC, and safe for human consumption in the edible parts of fish species in the regions.

  7. Theoretical exploration of the oxidative properties of a [(tren Me1)CuO2]+ adduct relevant to copper monooxygenase enzymes: insights into competitive dehydrogenation versus hydroxylation reaction pathways.

    de la Lande, Aurélien; Parisel, Olivier; Gérard, Hélène; Moliner, Vicente; Reinaud, Olivia


    Singlet and triplet H-transfer reaction paths from C-H and N-H bonds were examined by means of DFT and spin-flip TD-DFT computations on the [(tren Me1)CuO2]+ adduct. The singlet energy surfaces allow its evolution towards H2O2 and an imine species. Whereas N-H cleavage appears to be a radical process, C-H rupture results in a carbocation intermediate stabilized by an adjacent N atom and an electrostatic interaction with the [CuIOOH] metal core. Upon injection of an additional electron, the latter species straightforwardly forms a hydroxylated product. Based on these computational results, a new mechanistic description of the reactivity of copper monooxygenases is proposed.

  8. Coordination of NO(2)(-) ligand to Cu(I) ion in an O,O-bidentate fashion that evolves NO gas upon protonation: a model reaction relevant to the denitrification process.

    Chen, Chi-Shian; Yeh, Wen-Yann


    [(2,6-(Ph(2)P(o-C(6)H(4))CH=N)(2)C(5)H(3)N)(2)Cu(2)](BF(4))(2) (2) has been prepared by treating 2,6-(Ph(2)P(o-C(6)H(4))CH=N)(2)C(5)H(3)N (1) with [Cu(NCMe)(4)]BF(4). Reaction of 2 and [Ph(3)PNPPh(3)]NO(2) produces (2,6-(Ph(2)P(o-C(6)H(4))CH=N)(2)C(5)H(3)N)Cu(NO(2)) (3), with the nitrite ligand in a unique eta(2)-O,O coordination mode. Protonation of 3 releases NO gas, which mimics the reactivity of the Type 2 Cu-NiRs.

  9. Study of the reaction between {sup 51}CrO{sub 3} and concentrated nitric acid by radio chromatographic methods; Estudo da reacao entre {sup 51}CrO{sub 3} e acido nitrico concentrado por metodos radiocromatograficos

    Pezzin, Sergio H. [Univesidade do Estado de Santa Catarina (UDESC), Joinville, SC (Brazil). Centro de Ciencias Tecnologicas; Collins, Carol H.; Collins, Kenneth E. [Universidade Estadual de Campinas, SP (Brazil). Inst. de Quimica


    The objective of the present work is to verify the reduction of CrO{sub 3} in concentrated nitric acid, using {sup 51}Cr as a tracer. For the study, {sup 51}CrO{sub 3} (ca. 200,000 cpm/mg) was added to 65% HNO{sub 3} and maintained under agitation at 20 deg C for specified time periods. Aliquots (100 {mu}) were analyzed by open column cation (AG50Wx8, 100-200 mesh, Na{sup +} form) chromatography, either immediately or after dilution to approximately pH 2 and storage for specified time periods. The separations, which were made by stepwise elution using HClO{sub 4} and Ca(ClO{sub 4}){sub 2} solutions as effluents with fraction collection, followed by counting with a NaI(Tl) detector and a single channel analyzer. It was verified that ca. 3.5% of Cr(III) is obtained after 15 min of reaction. The major reaction product is hexaaquo chromium(III), with minor concentrations of mononitrate penta-aquochromium(III), [Cr(H{sub 2}O){sub 5}NO{sub 3}]{sup 2+}, a product which undergoes watering at pH 2 to produce, after 360 h, [Cr(H{sub 2}O){sub 6}]{sup 3+}. (author)

  10. Task relevance regulates the interaction between reward expectation and emotion.

    Wei, Ping; Kang, Guanlan


    In the present study, we investigated the impact of reward expectation on the processing of emotional facial expression using a cue-target paradigm. A cue indicating the reward condition of each trial (incentive vs. non-incentive) was followed by the presentation of a picture of an emotional face, the target. Participants were asked to discriminate the emotional expression of the target face in Experiment 1, to discriminate the gender of the target face in Experiment 2, and to judge a number superimposed on the center of the target face as even or odd in Experiment 3, rendering the emotional expression of the target face as task relevant in Experiment 1 but task irrelevant in Experiments 2 and 3. Faster reaction times (RTs) were observed in the monetary incentive condition than in the non-incentive condition, demonstrating the effect of reward on facilitating task concentration. Moreover, the reward effect (i.e., RTs in non-incentive conditions versus incentive conditions) was larger for emotional faces than for neutral faces when emotional expression was task relevant but not when it was task irrelevant. The findings suggest that top-down incentive motivation biased attentional processing toward task-relevant stimuli, and that task relevance played an important role in regulating the influence of reward expectation on the processing of emotional stimuli.

  11. Making Science Relevant

    Eick, Charles; Deutsch, Bill; Fuller, Jennifer; Scott, Fletcher


    Science teachers are always looking for ways to demonstrate the relevance of science to students. By connecting science learning to important societal issues, teachers can motivate students to both enjoy and engage in relevant science (Bennet, Lubben, and Hogarth 2007). To develop that connection, teachers can help students take an active role in…

  12. Excitation functions of proton-induced reactions on natural Nd in the 10-30 MeV energy range, and production of radionuclides relevant for double-{\\beta} decay

    Lebeda, O; Schrock, P; Štursa, J; Zuber, K; 10.1103/PhysRevC.85.014602


    A preferred candidate for neutrinoless double-{\\beta} decay, 150Nd, is present in natural neodymium at an abundance level of 5.64%. However, neodymium could be activated by cosmic rays during the period it spends on the Earth's surface. Its activation by protons is therefore of interest when it comes to estimating the possible disturbance effects and increased background during neutrinoless double-{\\beta}-decay experiments like Sudbury Neutrino Observatory plus liquid scintillator (SNO+). In most cases, we lack experimental data on proton-induced reactions on neodymium. Therefore, a measurement of cross sections has been performed for the formation of 141Pm, 143Pm, 144Pm, 146Pm, 148Pm, 148Pmm, 149Pm, 150Pm, 140Nd, 141Nd, 147Nd, 149Nd, 138Prm, 139Pr, 142Pr, and 139Ce by 10-30 MeV protons. Oxidation-protected metal foil targets of natural isotopic abundance were irradiated by the usual stacked-foil technique on the external proton beam of the isochronous cyclotron U-120M at the Nuclear Physics Institute at \\v{R...

  13. Criticisms of Relevance Theory

    尚静; 孟晔; 焦丽芳


    This paper briefly introduces first the notion of Sperber and Wilson's Relevance Theory. Then, the motivation of S & W putting forward their RT is also mentioned. Secondly, the paper gives some details about the methodology of RT, in which ostensive-inferential communication, context and optimal relevance are highlighted. Thirdly, the paper focuses on the criticisms of RT from different areas of research on human language and communication. Finally, the paper draws a conclusion on the great importance of RT in pragmatics.

  14. Mexico City normal weight children exposed to high concentrations of ambient PM2.5 show high blood leptin and endothelin-1, vitamin D deficiency, and food reward hormone dysregulation versus low pollution controls. Relevance for obesity and Alzheimer disease.

    Calderón-Garcidueñas, Lilian; Franco-Lira, Maricela; D'Angiulli, Amedeo; Rodríguez-Díaz, Joel; Blaurock-Busch, Eleonore; Busch, Yvette; Chao, Chih-kai; Thompson, Charles; Mukherjee, Partha S; Torres-Jardón, Ricardo; Perry, George


    Millions of Mexico, US and across the world children are overweight and obese. Exposure to fossil-fuel combustion sources increases the risk for obesity and diabetes, while long-term exposure to fine particulate matter (PM2.5) and ozone (O3) above US EPA standards is associated with increased risk of Alzheimer's disease (AD). Mexico City Metropolitan Area children are chronically exposed to PM2.5 and O3 concentrations above the standards and exhibit systemic, brain and intrathecal inflammation, cognitive deficits, and Alzheimer disease neuropathology. We investigated adipokines, food reward hormones, endothelial dysfunction, vitamin D and apolipoprotein E (APOE) relationships in 80 healthy, normal weight 11.1±3.2 year olds matched by age, gender, BMI and SES, low (n: 26) versus high (n:54) PM2.5 exposures. Mexico City children had higher leptin and endothelin-1 (pchildren. Mexico City APOE 4 versus 3 children had higher glucose (p=0.009). Serum 25-hydroxyvitamin DMexico City children. Leptin is strongly positively associated to PM 2.5 cumulative exposures. Residing in a high PM2.5 and O3 environment is associated with 12h fasting hyperleptinemia, altered appetite-regulating peptides, vitamin D deficiency, and increases in ET-1 in clinically healthy children. These changes could signal the future trajectory of urban children towards the development of insulin resistance, obesity, type II diabetes, premature cardiovascular disease, addiction-like behavior, cognitive impairment and Alzheimer's disease. Increased efforts should be made to decrease pediatric PM2.5 exposures, to deliver health interventions prior to the development of obesity and to identify and mitigate environmental factors influencing obesity and Alzheimer disease.

  15. Surface sampling concentration and reaction probe

    Van Berkel, Gary J; Elnaggar, Mariam S


    A method of analyzing a chemical composition of a specimen is described. The method can include providing a probe comprising an outer capillary tube and an inner capillary tube disposed co-axially within the outer capillary tube, where the inner and outer capillary tubes define a solvent capillary and a sampling capillary in fluid communication with one another at a distal end of the probe; contacting a target site on a surface of a specimen with a solvent in fluid communication with the probe; maintaining a plug volume proximate a solvent-specimen interface, wherein the plug volume is in fluid communication with the probe; draining plug sampling fluid from the plug volume through the sampling capillary; and analyzing a chemical composition of the plug sampling fluid with an analytical instrument. A system for performing the method is also described.

  16. Chemical reactions at aqueous interfaces

    Vecitis, Chad David


    Interfaces or phase boundaries are a unique chemical environment relative to individual gas, liquid, or solid phases. Interfacial reaction mechanisms and kinetics are often at variance with homogeneous chemistry due to mass transfer, molecular orientation, and catalytic effects. Aqueous interfaces are a common subject of environmental science and engineering research, and three environmentally relevant aqueous interfaces are investigated in this thesis: 1) fluorochemical sonochemistry (bubble-water), 2) aqueous aerosol ozonation (gas-water droplet), and 3) electrolytic hydrogen production and simultaneous organic oxidation (water-metal/semiconductor). Direct interfacial analysis under environmentally relevant conditions is difficult, since most surface-specific techniques require relatively `extreme' conditions. Thus, the experimental investigations here focus on the development of chemical reactors and analytical techniques for the completion of time/concentration-dependent measurements of reactants and their products. Kinetic modeling, estimations, and/or correlations were used to extract information on interfacially relevant processes. We found that interfacial chemistry was determined to be the rate-limiting step to a subsequent series of relatively fast homogeneous reactions, for example: 1) Pyrolytic cleavage of the ionic headgroup of perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) adsorbed to cavitating bubble-water interfaces during sonolysis was the rate-determining step in transformation to their inorganic constituents carbon monoxide, carbon dioxide, and fluoride; 2) ozone oxidation of aqueous iodide to hypoiodous acid at the aerosol-gas interface is the rate-determining step in the oxidation of bromide and chloride to dihalogens; 3) Electrolytic oxidation of anodic titanol surface groups is rate-limiting for the overall oxidation of organics by the dichloride radical. We also found chemistry unique to the interface, for example: 1

  17. The Limits to Relevance

    Averill, M.; Briggle, A.


    Science policy and knowledge production lately have taken a pragmatic turn. Funding agencies increasingly are requiring scientists to explain the relevance of their work to society. This stems in part from mounting critiques of the "linear model" of knowledge production in which scientists operating according to their own interests or disciplinary standards are presumed to automatically produce knowledge that is of relevance outside of their narrow communities. Many contend that funded scientific research should be linked more directly to societal goals, which implies a shift in the kind of research that will be funded. While both authors support the concept of useful science, we question the exact meaning of "relevance" and the wisdom of allowing it to control research agendas. We hope to contribute to the conversation by thinking more critically about the meaning and limits of the term "relevance" and the trade-offs implicit in a narrow utilitarian approach. The paper will consider which interests tend to be privileged by an emphasis on relevance and address issues such as whose goals ought to be pursued and why, and who gets to decide. We will consider how relevance, narrowly construed, may actually limit the ultimate utility of scientific research. The paper also will reflect on the worthiness of research goals themselves and their relationship to a broader view of what it means to be human and to live in society. Just as there is more to being human than the pragmatic demands of daily life, there is more at issue with knowledge production than finding the most efficient ways to satisfy consumer preferences or fix near-term policy problems. We will conclude by calling for a balanced approach to funding research that addresses society's most pressing needs but also supports innovative research with less immediately apparent application.

  18. The Relevance of Literature.

    Dunham, L. L.


    The "legacy" of the humanities is discussed in terms of relevance, involvement, and other philosophical considerations. Reasons for studying foreign literature in language classes are developed in the article. Comment is also made on attitudes and ideas culled from the writings of Clifton Fadiman, Jean Paul Sartre, and James Baldwin. (RL)

  19. Relevant Subspace Clustering

    Müller, Emmanuel; Assent, Ira; Günnemann, Stephan


    . We prove that computation of this model is NP-hard. For RESCU, we propose an approximative solution that shows high accuracy with respect to our relevance model. Thorough experiments on synthetic and real world data show that RESCU successfully reduces the result to manageable sizes. It reliably...... achieves top clustering quality while competing approaches show greatly varying performance....

  20. Is Information Still Relevant?

    Ma, Lia


    Introduction: The term "information" in information science does not share the characteristics of those of a nomenclature: it does not bear a generally accepted definition and it does not serve as the bases and assumptions for research studies. As the data deluge has arrived, is the concept of information still relevant for information…

  1. Relevant Subspace Clustering

    Müller, Emmanuel; Assent, Ira; Günnemann, Stephan;


    Subspace clustering aims at detecting clusters in any subspace projection of a high dimensional space. As the number of possible subspace projections is exponential in the number of dimensions, the result is often tremendously large. Recent approaches fail to reduce results to relevant subspace c...

  2. Sodium metabisulfite allergy is common but is it relevant?

    Madan, Vishal; Walker, Stephen L; Beck, Michael H


    Positive patch tests to sodium metabisulfite (SMB) are frequent. Standard series patch testing to SMB in 1751 patients showed 71 reactions interpreted as positive and allergic. 33 (46.5%) reactions were originally reported as relevant and 38 (53.5%) were of unexplained relevance depending on the presence or absence of identifiable sources responsible for the presenting dermatitis. A breakdown of these findings is presented. An additional detailed study of the sources of SMB in the environment and a retrospective analysis of these results have been undertaken to identify further, possibly overlooked sources of SMB exposure based on the occupational and recreational history. Most of the positive reactions in the relevant group were attributed to the use of Trimovate cream (63%). 5 patients (13%) with positive reactions in the unexplained relevance group were potentially exposed to SMB in local anaesthetic solutions while at work. 3 patients in the unexplained relevance group (7.8%) and 4 (12.1%) in the relevant group had potential for occupational exposure to SMB as bakers or caterers. Overall, occupational exposure was considered as a possible source of sensitization in 10 (26.3%) patients in the unexplained relevance group. We propose that sensitization to SMB from parenteral solutions and occupational exposure from food handling may account for some of the otherwise unexplained positive patch test reactions. A detailed occupational history should be therefore be sought in otherwise unexplained positive reactions to SMB. We also propose that it is worthwhile including SMB in our standard series in the UK.

  3. 锌-空气电池电解液Zn2+浓度对析氢过程的影响%Effects of Zn2+ concentration upon hydrogen evolution reaction for zinc-air battery

    马洪运; 范永生; 王保国


    水溶液体系的二次金属-空气电池通常具有安全环保的特点,但是充电过程中仍然存在析氢副反应的安全隐患。使用线性电势扫描方法、Tafel 极化曲线及极限扩散电流密度参数定量分析了二次锌-空气电池体系电解液中Zn2+浓度对析氢反应过程的影响。结果表明,随着电解液中Zn2+浓度的提高,析氢过电势逐渐增大,Zn2+浓度在6 mol·L-1 KOH溶液中达到0.4 mol·L-1时,析氢过电势超过2.42 V,析氢过电势比空白溶液提高1.2 V,并且Tafel极化曲线的截距超过1.5 V,析氢电势达到超高过电势范围。此外,由Zn2+提供的极限扩散电流密度提高至8.9 A·cm-2,所对应的过电势提高700 mV。研究结果对于确立二次锌-空气电池极限充电范围提供定量依据,对电池安全平稳运行具有重要价值。%Owing to the usage of water solution, the secondary metal-air batteries could be excellent for energy storage systems with outstanding advantages in high safety and environmental friendliness. However, the side reaction of hydrogen evolution in the water solution system is the potential hazard for the operation of batteries. In this study, the effects of Zn2+ concentration on hydrogen evolution reaction were investigated with the methods of linear sweep voltammetry, Tafel polarization curves and parameters of limiting diffusion current density for the zinc-air battery. The results showed that the overvoltage of hydrogen evolution reaction reached 2.42 V and the overpotential was 1.2 V higher than that in the blank solution when the concentration of Zn2+ in 6 mol·L-1 KOH solution was 0.4 mol·L-1. The intercept of the Tafel equation was more than 1.5 V, which suggests that the hydrogen evolution reaction for the solution containing 0.4 mol·L-1 Zn2+ reaches the super-overpotential range. The limiting diffusion current density reached 8.9 A·cm-2 and the overpotential was raised by 700 mV. These data are


    Fine particles and coarse particles are defined in terms of the modal structure of particle size distributions typically observed in the atmosphere. Differences among the various modes are discussed. The fractions of fine and coarse particles collected in specific size ranges, ...

  5. Clinical Relevance of Adipokines

    Matthias Blüher


    Full Text Available The incidence of obesity has increased dramatically during recent decades. Obesity increases the risk for metabolic and cardiovascular diseases and may therefore contribute to premature death. With increasing fat mass, secretion of adipose tissue derived bioactive molecules (adipokines changes towards a pro-inflammatory, diabetogenic and atherogenic pattern. Adipokines are involved in the regulation of appetite and satiety, energy expenditure, activity, endothelial function, hemostasis, blood pressure, insulin sensitivity, energy metabolism in insulin sensitive tissues, adipogenesis, fat distribution and insulin secretion in pancreatic β-cells. Therefore, adipokines are clinically relevant as biomarkers for fat distribution, adipose tissue function, liver fat content, insulin sensitivity, chronic inflammation and have the potential for future pharmacological treatment strategies for obesity and its related diseases. This review focuses on the clinical relevance of selected adipokines as markers or predictors of obesity related diseases and as potential therapeutic tools or targets in metabolic and cardiovascular diseases.

  6. Korrek, volledig, relevant

    Bergenholtz, Henning; Gouws, Rufus


    as detrimental to the status of a dictionary as a container of linguistic knowledge. This paper shows that, from a lexicographic perspective, such a distinction is not relevant. What is important is that definitions should contain information that is relevant to and needed by the target users of that specific......In explanatory dictionaries, both general language dictionaries and dictionaries dealing with languages for special purposes, the lexicographic definition is an important item to present the meaning of a given lemma. Due to a strong linguistic bias, resulting from an approach prevalent in the early...... phases of the development of theoretical lexicography, a distinction is often made between encyclopaedic information and semantic information in dictionary definitions, and dictionaries had often been criticized when their definitions were dominated by an encyclopaedic approach. This used to be seen...

  7. Information Needs/Relevance

    Wildemuth, Barbara M.


    A user's interaction with a DL is often initiated as the result of the user experiencing an information need of some kind. Aspects of that experience and how it might affect the user's interactions with the DL are discussed in this module. In addition, users continuously make decisions about and evaluations of the materials retrieved from a DL, relative to their information needs. Relevance judgments, and their relationship to the user's information needs, are discussed in this module. Draft

  8. Evaluation of an ethidium monoazide-enhanced 16S rDNA real-time polymerase chain reaction assay for bacterial screening of platelet concentrates and comparison with automated culture.

    Garson, Jeremy A; Patel, Poorvi; McDonald, Carl; Ball, Joanne; Rosenberg, Gillian; Tettmar, Kate I; Brailsford, Susan R; Pitt, Tyrone; Tedder, Richard S


    Culture-based systems are currently the preferred means for bacterial screening of platelet (PLT) concentrates. Alternative bacterial detection techniques based on nucleic acid amplification have also been developed but these have yet to be fully evaluated. In this study we evaluate a novel 16S rDNA polymerase chain reaction (PCR) assay and compare its performance with automated culture. A total of 2050 time-expired, 176 fresh, and 400 initial-reactive PLT packs were tested by real-time PCR using broadly reactive 16S primers and a "universal" probe (TaqMan, Invitrogen). PLTs were also tested using a microbial detection system (BacT/ALERT, bioMérieux) under aerobic and anaerobic conditions. Seven of 2050 (0.34%) time-expired PLTs were found repeat reactive by PCR on the initial nucleic acid extract but none of these was confirmed positive on testing frozen second aliquots. BacT/ALERT testing also failed to confirm any time-expired PLTs positive on repeat testing, although 0.24% were reactive on the first test. Three of the 400 "initial-reactive" PLT packs were found by both PCR and BacT/ALERT to be contaminated (Escherichia coli, Listeria monocytogenes, and Streptococcus vestibularis identified) and 14 additional packs were confirmed positive by BacT/ALERT only. In 13 of these cases the contaminating organisms were identified as anaerobic skin or oral commensals and the remaining pack was contaminated with Streptococcus pneumoniae. These results demonstrate that the 16S PCR assay is less sensitive than BacT/ALERT and inappropriate for early testing of concentrates. However, rapid PCR assays such as this may be suitable for a strategy of late or prerelease testing. © 2013 American Association of Blood Banks.

  9. The Progression of Sequential Reactions

    Jack McGeachy


    Full Text Available Sequential reactions consist of linked reactions in which the product of the first reaction becomes the substrate of a second reaction. Sequential reactions occur in industrially important processes, such as the chlorination of methane. A generalized series of three sequential reactions was analyzed in order to determine the times at which each chemical species reaches its maximum. To determine the concentration of each species as a function of time, the differential rate laws for each species were solved. The solution of each gave the concentration curve of the chemical species. The concentration curves of species A1 and A2 possessed discreet maxima, which were determined through slope-analysis. The concentration curve of the final product, A3, did not possess a discreet maximum, but rather approached a finite limit.

  10. Dynamic reaction design of enzymic biotransformations in organic media: equilibrium-controlled synthesis of antibiotics by penicillin G acylase.

    Fernandez-Lafuente, R; Rosell, C M; Guisan, J M


    Parameters relevant to the thermodynamically controlled synthesis of cephalothin utilizing highly active stabilized penicillin G acylase derivatives were studied. These included solubility/stability of substrates, enzyme derivative activity/stability, reaction course and synthetic yields. These parameters were altered by varying the pH, dimethylformamide concentration and temperature. Simultaneous optimization of the selected parameters could not be achieved with a single set of conditions. However, continuous adjustment of conditions throughout the reaction course allowed each parameter to be optimized (dynamic reaction design). This strategy works by optimizing those parameters that are critical to the overall reaction at a given point, whilst leaving others sub-optimal when their contribution to the total is minimal. This strategy has achieved a 90% transformation of antibiotic nucleus to cephalothin at a final concentration of 20 g/l, high enzyme and reactant stability, with a reaction period of 3 h (using 1 ml of derivative/40 ml of reaction solution).

  11. Variance-corrected Michaelis-Menten equation predicts transient rates of single-enzyme reactions and response times in bacterial gene-regulation

    Pulkkinen, O


    Many chemical reactions in biological cells occur at very low concentrations of constituent molecules. Thus, transcriptional gene-regulation is often controlled by poorly expressed transcription-factors, such as E.coli lac repressor with few tens of copies. Here we study the effects of inherent concentration fluctuations of substrate-molecules on the seminal Michaelis-Menten scheme of biochemical reactions. We present a universal correction to the Michaelis-Menten equation for the reaction-rates. The relevance and validity of this correction for enzymatic reactions and intracellular gene-regulation is demonstrated. Our analytical theory and simulation results confirm that the proposed variance-corrected Michaelis-Menten equation predicts the rate of reactions with remarkable accuracy even in the presence of large non-equilibrium concentration fluctuations. The major advantage of our approach is that it involves only the mean and variance of the substrate-molecule concentration. Our theory is therefore accessi...

  12. Chronobiology: relevance for tuberculosis.

    Santos, Lígia Gabrielle; Pires, Gabriel Natan; Azeredo Bittencourt, Lia Rita; Tufik, Sergio; Andersen, Monica Levy


    Despite the knowledge concerning the pathogenesis of tuberculosis, this disease remains one of the most important causes of mortality worldwide. Several risk factors are well-known, such poverty, HIV infection, and poor nutrition, among others. However, some issues that may influence tuberculosis warrant further investigation. In particular, the chronobiological aspects related to tuberculosis have garnered limited attention. In general, the interface between tuberculosis and chronobiology is manifested in four ways: variations in vitamin D bioavailability, winter conditions, associated infections, and circannual oscillations of lymphocytes activity. Moreover, tuberculosis is related to the following chronobiological factors: seasonality, latitude, photoperiod and radiation. Despite the relevance of these topics, the relationship between them has been weakly reviewed. This review aims to synthesize the studies regarding the association between tuberculosis and chronobiology, as well as urge critical discussion and highlight its applicability to health policies for tuberculosis.

  13. Reaction Graph



    The paper proposes reaction graphs as graphical representations of computational objects.A reaction graph is a directed graph with all its arrows and some of its nodes labeled.Computations are modled by graph rewriting of a simple nature.The basic rewriting rules embody the essence of both the communications among processes and cut-eliminations in proofs.Calculi of graphs are ideentified to give a formal and algebraic account of reaction graphs in the spirit of process algebra.With the help of the calculi,it is demonstrated that reaction graphs capture many interesting aspects of computations.

  14. Concentration device


    A concentration device (2) for filter filtration concentration of particles (4) from a volume of a fluid (6). The concentration device (2) comprises a filter (8) configured to filter particles (4) of a predefined size in the volume of the fluid (6). The concentration device (2) comprises...

  15. Concentrated Ownership

    Rose, Caspar


    , especially minority shareholders. Concentrated ownership is associated with benefits and costs. Concentrated ownership may reduce agency costs by increased monitoring of top management. However, concentrated ownership may also provide dominating owners with private benefits of control.......This entry summarizes the main theoretical contributions and empirical findings in relation to concentrated ownership from a law and economics perspective. The various forms of concentrated ownership are described as well as analyzed from the perspective of the legal protection of investors...

  16. Concentration risk

    Matić Vesna


    Full Text Available Concentration risk has been gaining a special dimension in the contemporary financial and economic environment. Financial institutions are exposed to this risk mainly in the field of lending, mostly through their credit activities and concentration of credit portfolios. This refers to the concentration of different exposures within a single risk category (credit risk, market risk, operational risk, liquidity risk.

  17. Examining Different Regions of Relevance: From Highly Relevant to Not Relevant.

    Spink, Amanda; Greisdorf, Howard; Bateman, Judy


    Proposes a useful concept of relevance as a relationship and an effect on the movement of a user through the iterative stages of their information seeking process, and that users' relevance judgments can be plotted on a Three-Dimensional Spatial Model of Relevance Level, Degree and Time. Discusses implications for the development of information…

  18. Explaining the atypical reaction profiles of heme enzymes with a novel mechanistic hypothesis and kinetic treatment.

    Kelath Murali Manoj

    Full Text Available Many heme enzymes show remarkable versatility and atypical kinetics. The fungal extracellular enzyme chloroperoxidase (CPO characterizes a variety of one and two electron redox reactions in the presence of hydroperoxides. A structural counterpart, found in mammalian microsomal cytochrome P450 (CYP, uses molecular oxygen plus NADPH for the oxidative metabolism (predominantly hydroxylation of substrate in conjunction with a redox partner enzyme, cytochrome P450 reductase. In this study, we employ the two above-mentioned heme-thiolate proteins to probe the reaction kinetics and mechanism of heme enzymes. Hitherto, a substrate inhibition model based upon non-productive binding of substrate (two-site model was used to account for the inhibition of reaction at higher substrate concentrations for the CYP reaction systems. Herein, the observation of substrate inhibition is shown for both peroxide and final substrate in CPO catalyzed peroxidations. Further, analogy is drawn in the "steady state kinetics" of CPO and CYP reaction systems. New experimental observations and analyses indicate that a scheme of competing reactions (involving primary product with enzyme or other reaction components/intermediates is relevant in such complex reaction mixtures. The presence of non-selective reactive intermediate(s affords alternate reaction routes at various substrate/product concentrations, thereby leading to a lowered detectable concentration of "the product of interest" in the reaction milieu. Occam's razor favors the new hypothesis. With the new hypothesis as foundation, a new biphasic treatment to analyze the kinetics is put forth. We also introduce a key concept of "substrate concentration at maximum observed rate". The new treatment affords a more acceptable fit for observable experimental kinetic data of heme redox enzymes.

  19. Leaching Mechanism of Complicated Antimony-Lead Concentrate and Sulfur Formation in Slurry Electrolysis

    WangChengyan; QiuDingfan; JiangPeihai


    Anodic reaction mechanism of complicated antimony-lead concentrate in slurry electrolysis was investigated by the anodic polarization curves determined under various conditions. The main reactions on the anode are the oxidations of FeCln(2-n) . Though the oxidation of jamesonite particle on the anode can occur during the whole process, it is less. With the help of mineralogy studies and relevant tests, the leaching reaction mechanism of jameson[to and gudmundite during slurry electrolysis was ascertained. Because of the oxidation reaction of FeCl3 produced by antimony-lead concentrate itself, the non-oxidation complex acid dissolution of jameson[re, the oxidation complex acid dissolution of gudmundite, and the oxidation of air carried by stirring, the leaching ratio of antimony reaches about 35% when HCl-NH4Cl solution is used to leach antimony-lead concentrate directly. So when the theoretical electric quantity is given to oxidation of antimony in slurry electrolysis, all of antimony, lead and iron containing in antimony-lead concentrate, are leached. The formation of sulfur is through the directly redox reaction of Fe3+ and jameson[re. The S2- in jamesonite is oxidized into S0 , and forms the crystals of sulfur again on the spot. The redox reaction of Fe3+ and H2S formed by non-oxidative acid dissolution of jamesonite is less.

  20. Carbon Concentration of Austenite

    Z. Ławrynowicz


    Full Text Available The investigation was carried out to examine the influence of temperature and times of austempering process on the maximum extend towhich the bainite reaction can proceed and the carbon content in retained austenite. It should be noted that a small percentage change in theaustenite carbon content can have a significant effect on the subsequent austempering reaction changing the volume fraction of the phasespresent and hence, the resulting mechanical properties. Specimens were prepared from an unalloyed ductile cast iron, austenitised at 950oCfor 60 minutes and austempered by the conventional single-step austempering process at four temperatures between BS and MS, eg., 250,300, 350 and 400oC. The samples were austempered at these temperatures for 15, 30, 60, 120 and 240 minutes and finally quenched toambient temperature. Volume fractions of retained austenite and carbon concentration in the residual austenite have been observed byusing X-ray diffraction. Additionally, carbon concentration in the residual austenite was calculated using volume fraction data of austeniteand a model developed by Bhadeshia based on the McLellan and Dunn quasi-chemical thermodynamic model. The comparison ofexperimental data with the T0, T0' and Ae3' phase boundaries suggests the likely mechanism of bainite reaction in cast iron is displacive rather than diffusional. The carbon concentration in retained austenite demonstrates that at the end of bainite reaction the microstructure must consist of not only ausferrite but additionally precipitated carbides.

  1. [Effect of air-electric fields on driving and reaction patterns. Test subjects in the car driving simulator (author's transl)].

    Anselm, D; Danner, M; Kirmaier, N; König, H L; Müller-Limmroth, W; Reis, A; Schauerte, W


    In the relevant frequency range of about 10 Hertz cars can be considered very largely as Faraday cages and consequently as screens against air-electric fields. This may have a negative influence on driving and reaction patterns as a result. In an extensive investigation 48 subjects in a driving simulator were exposed to definite artificially produced air-electric fields. The self-rating of the performance and concentration of the subjects, reaction times and driving errors were determined. While the reaction times remained practically constant, the driving behavior of the subjects improved.

  2. Ligand Exchange Kinetics of Environmentally Relevant Metals

    Panasci, Adele Frances [Univ. of California, Davis, CA (United States)


    The interactions of ground water with minerals and contaminants are of broad interest for geochemists but are not well understood. Experiments on the molecular scale can determine reaction parameters (i.e. rates of ligand exchange, activation entropy, activation entropy, and activation volume) that can be used in computations to gain insight into reactions that occur in natural groundwaters. Experiments to determine the rate of isotopic ligand exchange for three environmentally relevant metals, rhodium (Rh), iron (Fe), and neptunium (Np), are described. Many environmental transformations of metals (e.g. reduction) in soil occur at trivalent centers, Fe(III) in particular. Contaminant ions absorb to mineral surfaces via ligand exchange, and the reversal of this reaction can be dangerous, releasing contaminants into the environment. Ferric iron is difficult to study spectroscopically because most of its complexes are paramagnetic and are generally reactive toward ligand exchange; therefore, Rh(III), which is diamagnetic and less reactive, was used to study substitution reactions that are analogous to those that occur on mineral oxide surfaces. Studies on both Np(V) and Np(VI) are important in their own right, as 237Np is a radioactive transuranic element with a half-life of 2 million years.

  3. Power-law Fokker-Planck equation of unimolecular reaction based on the approximation to master equation

    Zhou, Yanjun; Yin, Cangtao


    The Fokker-Planck equation (FPE) of the unimolecular reaction with Tsallis distribution is established by means of approximation to the master equation. The memory effect, taken into transition probability, is relevant and important for lots of anomalous phenomena. The Taylor expansion for large volume is applied to derive the power-law FPE. The steady-state solution of FPE and microscopic dynamics Ito-Langevin equation of concentration variables are therefore obtained and discussed. Two unimolecular reactions are taken as examples and the concentration distributions with different power-law parameters are analyzed, which may imply strong memory effect of hopping process.

  4. User perspectives on relevance criteria

    Maglaughlin, Kelly L.; Sonnenwald, Diane H.


    matter, thought catalyst), full text (e.g., audience, novelty, type, possible content, utility), journal/publisher (e.g., novelty, main focus, perceived quality), and personal (e.g., competition, time requirements). Results further indicate that multiple criteria are used when making relevant, partially...... relevant, and not-relevant judgments, and that most criteria can have either a positive or negative contribution to the relevance of a document. The criteria most frequently mentioned by study participants were content, followed by criteria characterizing the full text document. These findings may have...... implications for relevance feedback in information retrieval systems, suggesting that systems accept and utilize multiple positive and negative relevance criteria from users. Systems designers may want to focus on supporting content criteria followed by full text criteria as these may provide the greatest cost...

  5. Relevance-driven Pragmatic Inferences



    Relevance theory, an inferential approach to pragmatics, claims that the hearer is expected to pick out the input of op-timal relevance from a mass of alternative inputs produced by the speaker in order to interpret the speaker ’s intentions. The de-gree of the relevance of an input can be assessed in terms of cognitive effects and the processing effort. The input of optimal rele-vance is the one yielding the greatest positive cognitive effect and requiring the least processing effort. This paper attempts to as-sess the degrees of the relevance of a mass of alternative inputs produced by an imaginary speaker from the perspective of her cor-responding hearer in terms of cognitive effects and the processing effort with a view to justifying the feasibility of the principle of relevance in pragmatic inferences.

  6. Goal relevance as a quantitative model of human task relevance.

    Tanner, James; Itti, Laurent


    The concept of relevance is used ubiquitously in everyday life. However, a general quantitative definition of relevance has been lacking, especially as pertains to quantifying the relevance of sensory observations to one's goals. We propose a theoretical definition for the information value of data observations with respect to a goal, which we call "goal relevance." We consider the probability distribution of an agent's subjective beliefs over how a goal can be achieved. When new data are observed, its goal relevance is measured as the Kullback-Leibler divergence between belief distributions before and after the observation. Theoretical predictions about the relevance of different obstacles in simulated environments agreed with the majority response of 38 human participants in 83.5% of trials, beating multiple machine-learning models. Our new definition of goal relevance is general, quantitative, explicit, and allows one to put a number onto the previously elusive notion of relevance of observations to a goal. (PsycINFO Database Record (c) 2017 APA, all rights reserved).

  7. Capture reactions

    Endt, P.M.


    Capture reactions will be considered here from the viewpoint of the nuclear spectroscopist. Especially important to him are the capture of neutrons, protons, and alpha particles, which may proceed through narrow resonances, offering a well defined initial state for the subsequent deexcitation proces

  8. Allergic Reactions

    ... round, they may be caused by exposure to indoor allergens such as dust mites, indoor molds or pets. Urticaria, or hives, is characterized ... home. Video: What is an allergic reaction? » Utility navigation Donate Annual meeting Browse your conditions Check pollen ...

  9. Signal Enhancement as Minimization of Relevant Information Loss

    Geiger, Bernhard C


    We introduce the notion of relevant information loss for the purpose of casting the signal enhancement problem in information-theoretic terms. We show that many algorithms from machine learning can be reformulated using relevant information loss, which allows their application to the aforementioned problem. As a particular example we analyze principle component analysis for dimensionality reduction, discuss its optimality, and show that the relevant information loss can indeed vanish if the relevant information is concentrated on a lower-dimensional subspace of the input space.

  10. Concentrating Radioactivity

    Herrmann, Richard A.


    By concentrating radioactivity contained on luminous dials, a teacher can make a high reading source for classroom experiments on radiation. The preparation of the source and its uses are described. (DT)

  11. Kinetics of the zinc anodic dissolution reaction in near neutral EDTA solutions



    Full Text Available Polarization curves of the anodic dissolution reaction of zinc were determined in EDTA solutions of different total molar concentrations (0.05, 0.10, 0.15 and 0.20 mol dm-3, the pH values of which were systematically varied (pH 3.0 – 10.0. The Tafel slopes of the anodic polarization curves are close to 40 mV dec-1 at lower current densities (10-5 – 5x10-4 A cm-2, while at higher current densities (5x10-4 – 10-2 A cm-2 the slopes are in the range of 60 – 120 mV dec-1. The order of the anodic reaction determined from the anodic polarization curves at lower current densities are: z+ (H+ ~ –1/2 for pH 8, while z+(H4Y ~ 1 for all pH values of the examined EDTA solutions. On the basis of these results, two mechanisms of the zinc anodic dissolution reaction are proposed: at pH 8. In both cases the relevant EDTA species directly participate as reactants in the anodic reaction. The dependences of the corrosion potential on pH and on total molar EDTA concentration indicate that the relevant EDTA species take part as reactants in both the cathodic (hydrogen evolution and anodic (zinc dissolution reactions of the zinc corrosion process.

  12. Automated microdroplet platform for sample manipulation and polymerase chain reaction.

    Chabert, Max; Dorfman, Kevin D; de Cremoux, Patricia; Roeraade, Johan; Viovy, Jean-Louis


    We present a fully automated system performing continuous sampling, reagent mixing, and polymerase chain reaction (PCR) in microdroplets transported in immiscible oil. Sample preparation and analysis are totally automated, using an original injection method from a modified 96-well plate layered with three superimposed liquid layers and in-capillary laser-induced fluorescence endpoint detection. The process is continuous, allowing sample droplets to be carried uninterruptedly into the reaction zone while new drops are aspirated from the sample plate. Reproducible amplification, negligible cross-contamination, and detection of low sample concentrations were demonstrated on numerous consecutive sample drops. The system, which opens the route to strong reagents and labor savings in high-throughput applications, was validated on the clinically relevant quantification of progesterone receptor gene expression in human breast cancer cell lines.

  13. Lexicography and the Relevance Criterion

    This will be done within the framework of the function theory .... work and made accessible through a rhyming system for the characters as well as a complex .... lexicographically relevant user characteristics — an open list to which new charac-.

  14. Relevance theory: pragmatics and cognition.

    Wearing, Catherine J


    Relevance Theory is a cognitively oriented theory of pragmatics, i.e., a theory of language use. It builds on the seminal work of H.P. Grice(1) to develop a pragmatic theory which is at once philosophically sensitive and empirically plausible (in both psychological and evolutionary terms). This entry reviews the central commitments and chief contributions of Relevance Theory, including its Gricean commitment to the centrality of intention-reading and inference in communication; the cognitively grounded notion of relevance which provides the mechanism for explaining pragmatic interpretation as an intention-driven, inferential process; and several key applications of the theory (lexical pragmatics, metaphor and irony, procedural meaning). Relevance Theory is an important contribution to our understanding of the pragmatics of communication.

  15. Relevance theory and pragmatic impairment.

    Leinonen, E; Kerbel, D


    This paper summarizes aspects of relevance theory that are useful for exploring impairment of pragmatic comprehension in children. It explores data from three children with pragmatic language difficulties within this framework. Relevance theory is seen to provide a means of explaining why, in a given context, a particular utterance is problematic. It thus enables one to move on from mere description of problematic behaviours towards their explanation. The theory provides a clearer delineation between the explicit and the implicit, and hence between semantics and pragmatics. This enables one to place certain difficulties more firmly within semantics and others within pragmatics. Relevance, and its maximization in communication, are squarely placed within human cognition, which suggests a close connection between pragmatic and cognitive (dis)functioning. Relevance theory thus emerges as a powerful tool in the exploration and understanding of pragmatic language difficulties in children and offers therapeutically valuable insight into the nature of interactions involving individuals with such impairments.

  16. Clinical relevance in anesthesia journals

    Lauritsen, Jakob; Møller, Ann M


    The purpose of this review is to present the latest knowledge and research on the definition and distribution of clinically relevant articles in anesthesia journals. It will also discuss the importance of the chosen methodology and outcome of articles.......The purpose of this review is to present the latest knowledge and research on the definition and distribution of clinically relevant articles in anesthesia journals. It will also discuss the importance of the chosen methodology and outcome of articles....

  17. Quantifying mixing using equilibrium reactions

    Wheat, Philip M.; Posner, Jonathan D.


    A method of quantifying equilibrium reactions in a microchannel using a fluorometric reaction of Fluo-4 and Ca2+ ions is presented. Under the proper conditions, equilibrium reactions can be used to quantify fluid mixing without the challenges associated with constituent mixing measures such as limited imaging spatial resolution and viewing angle coupled with three-dimensional structure. Quantitative measurements of CaCl and calcium-indicating fluorescent dye Fluo-4 mixing are measured in Y-shaped microchannels. Reactant and product concentration distributions are modeled using Green's function solutions and a numerical solution to the advection-diffusion equation. Equilibrium reactions provide for an unambiguous, quantitative measure of mixing when the reactant concentrations are greater than 100 times their dissociation constant and the diffusivities are equal. At lower concentrations and for dissimilar diffusivities, the area averaged fluorescence signal reaches a maximum before the species have interdiffused, suggesting that reactant concentrations and diffusivities must be carefully selected to provide unambiguous, quantitative mixing measures. Fluorometric equilibrium reactions work over a wide range of pH and background concentrations such that they can be used for a wide variety of fluid mixing measures including industrial or microscale flows.

  18. X-ray spectroscopic characterization of Co(IV) and metal–metal interactions in Co4O4: Electronic structure contributions to the formation of high-valent states relevant to the oxygen evolution reaction

    Hadt, Ryan G.; Hayes, Dugan; Brodsky, Casey N.; Ullman, Andrew M.; Casa, Diego M.; Upton, Mary H.; Nocera, Daniel G; Chen, Lin X.


    In this paper, the formation of high-valent states is a key factor in making highly active transition metal-based catalysts of the oxygen-evolving reaction (OER). These high oxidation states will be strongly influenced by the local geometric and electronic structures of the metal ion, which is difficult to study due to spectroscopically active and complex backgrounds, short lifetimes, and limited concentrations. Here, we use a wide range of complementary X-ray spectroscopies coupled to DFT calculations to study Co4O4 cubanes, which provide insight into the high-valent Co(IV) centers responsible for the activity of molecular and heterogeneous OER catalysts. The combination of X-ray absorption and 1s3p resonant inelastic X-ray scattering (Kβ RIXS) allow Co(IV) to be isolated and studied against a spectroscopically active Co(III) background. Co K- and L-edge X-ray absorption data allow for a detailed characterization of the 3d-manifold of effectively localized Co(IV) centers and provide a direct handle on the ligand field environment and covalency of the t2g-based redox active molecular orbital. Kβ RIXS is also shown to provide a powerful probe of Co(IV), and specific spectral features are sensitive to the degree of oxo-mediated metal-metal coupling across Co4O4. Guided by the data, calculations show electron-hole delocalization can actually oppose Co(IV) formation. Computational extension of Co4O4 to CoM3O4 structures (M = redox-inactive metal) defines electronic structure contri-butions to Co(IV) formation. Redox activity is shown to be linearly related to covalency, and M(III) oxo inductive effects on Co(IV) oxo bonding can tune the covalency of high-valent sites over a large range and thereby tune E0 over hundreds of mVs.

  19. Spallation reactions; Reactions de spallation

    Cugon, J.


    Spallation reactions dominate the interactions of hadrons with nuclei in the GeV range (from {approx} 0.1 to {approx} 10 GeV). They correspond to a sometimes important ejection of light particles leaving most of the time a residue of mass commensurate with the target mass. The main features of the experimental data are briefly reviewed. The most successful theoretical model, namely the intranuclear cascade + evaporation model, is presented. Its physical content, results and possible improvements are critically discussed. Alternative approaches are shortly reviewed. (author). 84 refs.

  20. Communication: Equilibrium rate coefficients from atomistic simulations: The O({sup 3}P) + NO({sup 2}Π) → O{sub 2}(X{sup 3}Σ{sub g}{sup −}) + N({sup 4}S) reaction at temperatures relevant to the hypersonic flight regime

    Castro-Palacio, Juan Carlos [Department of Chemistry, University of Basel, Klingelbergstrasse 80, 4056 Basel (Switzerland); Bemish, Raymond J. [Air Force Research Laboratory, Space Vehicles Directorate, Kirtland AFB, New Mexico 87117 (United States); Meuwly, Markus, E-mail: [Department of Chemistry, University of Basel, Klingelbergstrasse 80, 4056 Basel (Switzerland); Department of Chemistry, Brown University, Providence, Rhode Island 02912 (United States)


    The O({sup 3}P) + NO({sup 2}Π) → O{sub 2}(X{sup 3}Σ{sub g}{sup −}) + N({sup 4}S) reaction is among the N- and O- involving reactions that dominate the energetics of the reactive air flow around spacecraft during hypersonic atmospheric re-entry. In this regime, the temperature in the bow shock typically ranges from 1000 to 20 000 K. The forward and reverse rate coefficients for this reaction derived directly from trajectory calculations over this range of temperature are reported in this letter. Results compare well with the established equilibrium constants for the same reaction from thermodynamic quantities derived from spectroscopy in the gas phase which paves the way for large-scale in silico investigations of equilibrium rates under extreme conditions.

  1. Modelling of chalcopyrite oxidation reactions in the Outokumpu flash smelting process

    Ahokainen, T.; Jokilaakso, A. [Helsinki Univ. of Technology, Otaniemi (Finland)


    A mathematical model for simulating oxidation reactions of chalcopyrite particles together with momentum, heat and mass transfer between particle and gas phase in a flash smelting furnace reaction shaft is presented. In simulation, the equations governing the gas flow are solved numerically with a commercial fluid flow package, Phoenics. The particle phase is introduced into the gas flow by a Particle Source In Cell (PSIC) - technique, where a number of discrete particles is tracked in a gas flow and the relevant source terms for momentum, mass, and heat transfer are added to the gas phase equations. The gas phase equations used are elliptic in nature and the fluid turbulence is described by the (k-{epsilon}) -model. Thermal gas phase radiation is simulated with a six-flux radiation model. The chemical reactions of concentrate particles are assumed to happen at two sharp interfaces, and a shrinking core model is applied to describe the mass transfer of chemical species through the reaction product layer. In a molten state, the oxygen consumption is controlled by a film penetration concept. The reacting concentrate particles are a mixture of chalcopyrite and silica. Also a certain amount of pure inert silica is fed to the process as flux. In the simulations the calculation domain includes the concentrate burner and a cylindrical reaction shaft of an industrial scale flash smelting furnace. Some examples about the simulations carried out by the combustion model are presented. (author)

  2. Background defining during the imine formation reaction in FT-IR liquid cell

    Namli, Hilmi; Turhan, Onur


    Imine formation is a very important chemical reaction because of its relevance to biological process. Therefore, it is crucial to follow whole reaction process in detail. The current work performed to monitor the whole imination reaction in real time in liquid cell by FT-IR spectroscopy. The complex spectral futures due to solvent, unreacted reagents, acid catalysis and other additives are eliminated by defining a background at the beginning or at any time during the reaction. This procedure also makes it possible to monitor the changes in the concentration of each component in the liquid cell. The consumption of the functional groups of the reagents results in absorbance due to the direct difference spectra while the appearance of functional groups is monitored as percentage transmittance. The concentration changes in the cell arising from the reaction gives the product spectra without having to isolate it from the mixture. It is also possible to see the intermediates appearing and disappearing during the reaction. This report also illustrates a brief application of the technique by time dependence of the peak highs in absorption (ABS) mode.

  3. Reaction dynamics analysis of a reconstituted Escherichia coli protein translation system by computational modeling.

    Matsuura, Tomoaki; Tanimura, Naoki; Hosoda, Kazufumi; Yomo, Tetsuya; Shimizu, Yoshihiro


    To elucidate the dynamic features of a biologically relevant large-scale reaction network, we constructed a computational model of minimal protein synthesis consisting of 241 components and 968 reactions that synthesize the Met-Gly-Gly (MGG) peptide based on an Escherichia coli-based reconstituted in vitro protein synthesis system. We performed a simulation using parameters collected primarily from the literature and found that the rate of MGG peptide synthesis becomes nearly constant in minutes, thus achieving a steady state similar to experimental observations. In addition, concentration changes to 70% of the components, including intermediates, reached a plateau in a few minutes. However, the concentration change of each component exhibits several temporal plateaus, or a quasi-stationary state (QSS), before reaching the final plateau. To understand these complex dynamics, we focused on whether the components reached a QSS, mapped the arrangement of components in a QSS in the entire reaction network structure, and investigated time-dependent changes. We found that components in a QSS form clusters that grow over time but not in a linear fashion, and that this process involves the collapse and regrowth of clusters before the formation of a final large single cluster. These observations might commonly occur in other large-scale biological reaction networks. This developed analysis might be useful for understanding large-scale biological reactions by visualizing complex dynamics, thereby extracting the characteristics of the reaction network, including phase transitions.

  4. Regularization in Matrix Relevance Learning

    Schneider, Petra; Bunte, Kerstin; Stiekema, Han; Hammer, Barbara; Villmann, Thomas; Biehl, Michael


    A In this paper, we present a regularization technique to extend recently proposed matrix learning schemes in learning vector quantization (LVQ). These learning algorithms extend the concept of adaptive distance measures in LVQ to the use of relevance matrices. In general, metric learning can displa

  5. Advances in the quantification of relevant allergens in allergenic extracts.

    Batard, T; Nony, E; Hrabina, M; Chabre, H; Frati, F; Moingeon, P


    Relevant allergens are major contributors to the safety and efficacy of allergenic extracts used in allergen immunotherapy (AIT). As such, they should be accurately quantified, as recommended by the 2008 European guidelines on allergen products. Until now, the quantification of relevant allergens was mainly performed by using immunoassays (e.g. ELISA) that relying upon specific antibodies. Although antibody-based quantification is commonly used to assess the concentration of relevant allergens in allergenic extracts, results must be taken with caution in the light of the inherent limitations of such techniques. In the present study, we discuss how those limitations can be overcome by using comprehensive mass spectrometry-based techniques.

  6. Comparison of secondary organic aerosol formed with an aerosol flow reactor and environmental reaction chambers: effect of oxidant concentration, exposure time and seed particles on chemical composition and yield

    A. T. Lambe


    Full Text Available We performed a systematic intercomparison study of the chemistry and yields of SOA generated from OH oxidation of a common set of gas-phase precursors in a Potential Aerosol Mass (PAM continuous flow reactor and several environmental chambers. In the flow reactor, SOA precursors were oxidized using OH concentrations ranging from 2.0×108 to 2.2×1010 molec cm−3 over exposure times of 100 s. In the environmental chambers, precursors were oxidized using OH concentrations ranging from 2×106 to 2×107 molec cm−3 over exposure times of several hours. The OH concentration in the chamber experiments is close to that found in the atmosphere, but the integrated OH exposure in the flow reactor can simulate atmospheric exposure times of multiple days compared to chamber exposure times of only a day or so. A linear correlation analysis of the mass spectra (m=0.91–0.92, r2=0.93–0.94 and carbon oxidation state (m=1.1, r2=0.58 of SOA produced in the flow reactor and environmental chambers for OH exposures of approximately 1011 molec cm−3 s suggests that the composition of SOA produced in the flow reactor and chambers is the same within experimental accuracy as measured with an aerosol mass spectrometer. This similarity in turn suggests that both in the flow reactor and in chambers, SOA chemical composition at low OH exposure is governed primarily by gas-phase OH oxidation of the precursors, rather than heterogeneous oxidation of the condensed particles. In general, SOA yields measured in the flow reactor are lower than measured in chambers for the range of equivalent OH exposures that can be measured in both the flow reactor and chambers. The influence of sulfate seed particles on isoprene SOA yield measurements was examined in the flow reactor. The studies show that seed particles increase the yield of SOA produced in flow reactors by a factor of 3 to 5 and may also account in part for higher SOA yields obtained in the chambers, where seed

  7. Heuristics-Guided Exploration of Reaction Mechanisms

    Bergeler, Maike; Proppe, Jonny; Reiher, Markus


    For the investigation of chemical reaction networks, the efficient and accurate determination of all relevant intermediates and elementary reactions is inevitable. The complexity of such a network may grow rapidly, in particular if reactive species are involved that might cause a myriad of side reactions. Without automation, a complete investigation of complex reaction mechanisms is tedious and possibly unfeasible. Therefore, only the expected dominant reaction paths of a chemical reaction network (e.g., a catalytic cycle or an enzymatic cascade) are usually explored in practice. Here, we present a computational protocol that constructs such networks in a parallelized and automated manner. Molecular structures of reactive complexes are generated based on heuristic rules and subsequently optimized by electronic-structure methods. Pairs of reactive complexes related by an elementary reaction are then automatically detected and subjected to an automated search for the connecting transition state. The results are...

  8. Kinetic modelling of GlmU reactions - prioritization of reaction for therapeutic application.

    Vivek K Singh

    Full Text Available Mycobacterium tuberculosis(Mtu, a successful pathogen, has developed resistance against the existing anti-tubercular drugs necessitating discovery of drugs with novel action. Enzymes involved in peptidoglycan biosynthesis are attractive targets for antibacterial drug discovery. The bifunctional enzyme mycobacterial GlmU (Glucosamine 1-phosphate N-acetyltransferase/ N-acetylglucosamine-1-phosphate uridyltransferase has been a target enzyme for drug discovery. Its C- and N- terminal domains catalyze acetyltransferase (rxn-1 and uridyltransferase (rxn-2 activities respectively and the final product is involved in peptidoglycan synthesis. However, the bifunctional nature of GlmU poses difficulty in deciding which function to be intervened for therapeutic advantage. Genetic analysis showed this as an essential gene but it is still unclear whether any one or both of the activities are critical for cell survival. Often enzymatic activity with suitable high-throughput assay is chosen for random screening, which may not be the appropriate biological function inhibited for maximal effect. Prediction of rate-limiting function by dynamic network analysis of reactions could be an option to identify the appropriate function. With a view to provide insights into biochemical assays with appropriate activity for inhibitor screening, kinetic modelling studies on GlmU were undertaken. Kinetic model of Mtu GlmU-catalyzed reactions was built based on the available kinetic data on Mtu and deduction from Escherichia coli data. Several model variants were constructed including coupled/decoupled, varying metabolite concentrations and presence/absence of product inhibitions. This study demonstrates that in coupled model at low metabolite concentrations, inhibition of either of the GlmU reactions cause significant decrement in the overall GlmU rate. However at higher metabolite concentrations, rxn-2 showed higher decrement. Moreover, with available intracellular

  9. A unified diabatic description for electron transfer reactions, isomerization reactions, proton transfer reactions, and aromaticity.

    Reimers, Jeffrey R; McKemmish, Laura K; McKenzie, Ross H; Hush, Noel S


    While diabatic approaches are ubiquitous for the understanding of electron-transfer reactions and have been mooted as being of general relevance, alternate applications have not been able to unify the same wide range of observed spectroscopic and kinetic properties. The cause of this is identified as the fundamentally different orbital configurations involved: charge-transfer phenomena involve typically either 1 or 3 electrons in two orbitals whereas most reactions are typically closed shell. As a result, two vibrationally coupled electronic states depict charge-transfer scenarios whereas three coupled states arise for closed-shell reactions of non-degenerate molecules and seven states for the reactions implicated in the aromaticity of benzene. Previous diabatic treatments of closed-shell processes have considered only two arbitrarily chosen states as being critical, mapping these states to those for electron transfer. We show that such effective two-state diabatic models are feasible but involve renormalized electronic coupling and vibrational coupling parameters, with this renormalization being property dependent. With this caveat, diabatic models are shown to provide excellent descriptions of the spectroscopy and kinetics of the ammonia inversion reaction, proton transfer in N2H7(+), and aromaticity in benzene. This allows for the development of a single simple theory that can semi-quantitatively describe all of these chemical phenomena, as well as of course electron-transfer reactions. It forms a basis for understanding many technologically relevant aspects of chemical reactions, condensed-matter physics, chemical quantum entanglement, nanotechnology, and natural or artificial solar energy capture and conversion.

  10. Studies relevant to the catalytic activation of carbon monoxide

    Ford, P.C.


    Research activity during the 1991--1992 funding period has been concerned with the following topics relevant to carbon monoxide activation. (1) Exploratory studies of water gas shift catalysts heterogenized on polystyrene based polymers. (2) Mechanistic investigation of the nucleophilic activation of CO in metal carbonyl clusters. (3) Application of fast reaction techniques to prepare and to investigate reactive organometallic intermediates relevant to the activation of hydrocarbons toward carbonylation and to the formation of carbon-carbon bonds via the migratory insertion of CO into metal alkyl bonds.

  11. The oxygen evolution reaction on cobalt Part I. Reaction order experiments and impedance measurements

    Kobussen, A.G.C.; Willems, H.; Wit, J.H.W. de; Broers, G.H.J.


    It was found that the oxygen evolution reaction on cobalt in concentrated KOH solutions can be described differently for low and high overpotentials. In the overpotential range from 150 to 280 mV, the reaction has a Tafel slope of approximately 40 mV and a reaction order with respect to the KOH acti

  12. Cleaner concentrates

    Boudechiche, S.; Hall, S. [University of Nottingham, Nottingham (United Kingdom)


    The desire for higher quality coal products in froth flotation has led to the introduction of a number of novel flotation techniques, including flotation columns, but the benefits of each in relation to the source of the slurry must be evaluated before plant is installed. It was to assess on a laboratory scale the quality of coal flotation concentrates from column flotation of fine coal (-500{mu}m) as an alternative to the traditional conventional agitated cell that this work was carried out. The column developed specifically for this purpose allowed the establishment of an approach to the examination of the flotation response of samples of UK coals (originating from Bolsover, Derbyshies; Rawdon, Leicestershire; and Bilsthorpe, Nottinghamshire). The work indicates the importance of the origin of the feed slurry, since each type of coal exhibits a different flotation response. The observations from the results described in this paper enable an assessment to be made of the merits of column flotation in fine coal treatment. 11 refs., 4 figs., 5 tabs.

  13. Brief Review on the Relevance Theory

    龚腾龙; 阿勒腾


    Relevance theory has had an impact on the study in various disciplines including linguistics,literature and so on. This paper gives a brief review of the relevance theory and two principles of relevance.

  14. Topaz concentrate desiliconization with ammonium bifluoride

    Andreev, V. A.; Buynovskiy, A. S.; Andreev, Artyom Andreevich; Dyachenko, Alexander Nikolaevich


    Fluoridizing agent for the process of topaz concentrate desiliconization has been selected, topaz thermodynamic potentials have been appraised, thermodynamic probabilities of fluorination reaction of topaz concentrate main constituents have been calculated. The results of studying the concentrate desiliconization process with ammonium bifluoride by the methods of thermogravimetry, RFA, microphotography are presented

  15. Diagnostic relevance of uric acid


    Uric acid, the final product of purine metabolism, is one of the most recognized biological markers, a catalyzed reaction by xantina oxidoreductasa (XOR). This bifunctional enzyme in its dehydrogenated shape (XDH), produces AU, and nicotidamide adenine dinucleotide and in oxidase (XO), AU and Superoxide (O2•-). Hyperuricemia (HAU) is an indicator of over-regulation of XO activity, a powerful system producer of species of reactive oxygen (ROS), in human physiology. Accumulation of these radica...

  16. 环境相关浓度MC-LR作用对营养生长期水稻生长和抗氧化酶活性的影响%Effects of Microcystin-LR at Environmental Relevant Concentrations on Growth and Antioxidant Enzymes of Oryza sativa L. at Vegetative Stage

    张敏敏; 姜锦林; 周军英; 单正军; 卜元卿; 续卫利


    In recent years, the worldwide occurrence of cyanobacterial blooms is of great ecological concern because many genera of bloom-forming cyanobaceria are known to produce microcystins. Toxic effects of microcystin-LR(MC-LR)on mammals, birds, and aquatic organ-isms have been widely investigated, but its phytotoxic effects and mechanisms in terrestrial plants remain unclear. In the present study, we examined the growth and development and enzyme activities, including plant height, root length, aboveground biomass, photosynthesizer, and root peroxidase(POD), glutathione(GSH), protein phosphatase(PP)and malondialdehyde(MDA)in rice plants(Oryza sativa L.)ex-posed to 0, 0.1, 1, 10, 50μg·L-1 of MC-LR for 7, 15, 20, and 34 days. Results showed that the root length of rice increased by 6.94%and 6.06%under the exposure of 0.1 and 1μg·L-1 MC-LR, respectively, but reduced significantly by 8.71%under the exposure of 50μg·L-1 MC-LR, compared with the control over the 34 days of the experiment. MC-LR significantly induced the activities of some key indicators in the antioxidant system of rice, such as POD and GSH. The longer exposure time, the more remarkable induction was observed. However, POD was significantly inhibited by 58.51%and 8.09%by 0.1μg·L-1 MC-LR in 20 and 34 days of the experiment, respectively. Applying 50μg·L-1 MC-LR significantly inhibited POD, GSH, and PP by 38.52%, 45.86%, and 52.51%, respectively, after 34 days of the exposure. These results show that MC-LR has toxic effects on terrestrial plants under long time exposure to environmental relevant concentrations.%以水稻为受试生物,考察暴露浓度为0、0.1、1、10、50μg·L-1的MC-LR分别水培暴露7、15、20、34 d对水稻生长和根部部分酶活性的影响,考察指标包括水稻的株高、根长、鲜重、光合作用系统以及根系中过氧化物酶、谷胱甘肽酶、蛋白磷酸酶和丙二醛活性。34 d实验结束后,相比对照组,0.1、1μg·L-1 MC-LR作

  17. 肝细胞生长因子mRNA实时荧光定量PCR检测体系的建立及其在淋巴瘤诊断中的价值%Establishment of real-time fluorescence quantitative polymerase chain reaction analysis assay quantification for hepatocyte growth flactor mRNA expression and its clinical relevance in lymphoma

    岑东; 吕建新; 裴仁治; 涂植光; 余晓林; 文阳安


    Objective To construct quantitative standard for quantification of hepatocyte growth factor (HGF) mRNA and establish its real-time fluorescence quantitative(FQ)-PCR assay to estimate its clinical relevance in lymphoma.Methods Recombinant plasmid Was constructed with target cDNA obtained from isolated total RNA by RT-PCR After PCR products were identified and purified,recombined plasmids were quantitated and then acted as quantitative standard.A new real time FQ-PCR analysis system Was established with the second pair of primers and the probe after amplification condition and the concentrations of components were optimized.HGF mRNA expressions in 47 lymohoma cases[11 Hodgkin disease(HD) cases,36 non-Hodgkin lyphoma(NHL)cases.among these patients,36 patients in remission while 11 patients without remission ] were analyzed quantitatively,and its specificity and sensitivity for lymphoma diagnosis were evaluated by receiptor operation character(ROC)curve method.Results HGF mRNA quantitative standard was constructed successfully.and its real time FO.PCR analysis system Was established combined with hot.start PCR and down.touch PCR technique. According to slope of standard curve (-3.513)and correlation cofficient(0.999),amplification efficiency of the system was 92.6%.Coefficient variation of intra-assay,intra-day and inter-day-assay were 2.1%,4.0% and 6.8%,respectively.Sensitivity of FQ-PCR Was 2 eopies/μl.Expressions of HGF mRNA in lymphoma group Was higher than that in control group(6.425±2.172 and 0.317±0.192,respectively,t=15.883,P0.05).According to ROC analysis,its sensitivity and specificity were 93.6% and 100% when cutoff value for lymphoma clinical diagnosis Was 3.136.Conclusion HGF mRNA'8 quantitative standard and its real time F9-PCR analysis system have been successfully constructed,and it can be used for quantitative detection of its mRNA expression in lymphoma.%目的 构建肝细胞生长因子(HGF)mRNA定量标准,建立实时荧光定量(FQ)-PCR检测

  18. The effect of outside conditions on anaerobic ammonia oxidation reaction

    YANG Min; WANG Shu-bo


    Organic carbon, inorganic carbon, temperature, pH and ORP are all to have a certain influence on the anaerobic ammonia oxidation reaction. We can draw some conclusions on the optimum conditions of anaerobic ammonia oxidation reaction. The optimum temperature of the anaerobic ammonia oxidation reaction is 30-35℃. And the optimum pH of the anaerobic ammonia reaction is 7.5-8.3. The presence of organic matters can affect the anaerobic ammonia reaction, and different organic matters have different influence on it. The concentration of the inorganic carbon also exist great influence on the reaction. High inorganic carbon concentration also can inhibit anaerobic ammonia oxidation reaction.

  19. 低品位钼精矿氧化焙烧过程的反应行为%Reaction behavior of low grade molybdenum concentrates in oxidation roasting process

    甘敏; 范晓慧; 张麟; 姜涛; 邱冠周; 王勇; 邓琼; 陈许玲


    Thermodynamics of oxidation roasting, phase evolution rules and roasting characteristics of low grade molybdenum concentrate with grade of 39.27% were studied. Thermodynamics analyses show that the oxidation tendency of MoS 2 is second to that of FeS 2 , so it is easily oxidized and generates several oxide products. Furthermore, MoO 3 could react with various metal oxides to generate molybdate in which calcium molybdate generates most easily. Roasting process contains three stages of incomplete oxidization of MoS 2 , stable existence of MoO 3 and generation of molybdate. Molybdate and low valence molybdenum oxide, which go against subsequent leaching, will easily generate at over high temperature or for long time. The suitable temperature is 650−675 ℃ and the roasting time is 2 h. After roasting, ammonia leaching rate of molybdenum is only about 84.02%, residue of Mo in leaching residue reaches 13.93%. XRD analysis shows that calcium molybdate is the main component in leaching residue. When Na2CO3 is used as the leaching reagent, calcium molybdate can be extracted during leaching residue, and the ultimate recovery rate of Mo can reach 90.82%.%研究品位为39.27%的低品位钼精矿的氧化焙烧热力学、物相演变规律及焙烧特征。热力学分析表明:MoS 2氧化的趋势仅次于FeS 2氧化趋势,能生成多种价态的氧化物,且生成的MoO 3可与多种金属氧化物反应生成钼酸盐,其中生成钼酸钙的趋势最大。焙烧过程包括MoS 2氧化不充分、MoO 3稳定存在和钼酸盐生成3个阶段,温度过高或时间过长易生成不利于后续钼溶出的钼酸盐和低价氧化钼,适宜的焙烧温度为650~675℃、焙烧时间为2 h左右。氧化焙烧后,氨浸的钼溶出率仅为84.02%,浸出渣中钼含量高达13.93%,XRD分析表明浸出渣的组成以钼酸钙为主。采用Na 2 CO 3为浸出剂对氨浸渣进行二次浸出,可将氨浸渣中的钼酸钙溶出,

  20. Situating relevance: exploring individual relevance assessments in context

    Theresa Dirndorfer Anderson


    Full Text Available This paper discusses some of the challenges encountered whilst researching and writing a thesis that explores individual understandings of relevance and topic. It is based upon a discussion paper and presentation prepared as part of the Doctoral Workshop held during the ISIC 2000 Conference in Borås, Sweden. The focus of this paper is the doing of qualitative research. To provide a framework for this discussion, the key assumptions that have shaped the author's thesis are presented in the first section of this paper. The paper then focuses on some of the dilemmas of qualitative research encountered during the research and writing of this thesis, giving particular attention to the notion of context and the writing of qualitative research. Forthcoming results from the thesis are mentioned in the closing section. A Thesis Summary is also provided at the end of this paper.

  1. Theoretical studies of chemical reaction dynamics

    Schatz, G.C. [Argonne National Laboratory, IL (United States)


    This collaborative program with the Theoretical Chemistry Group at Argonne involves theoretical studies of gas phase chemical reactions and related energy transfer and photodissociation processes. Many of the reactions studied are of direct relevance to combustion; others are selected they provide important examples of special dynamical processes, or are of relevance to experimental measurements. Both classical trajectory and quantum reactive scattering methods are used for these studies, and the types of information determined range from thermal rate constants to state to state differential cross sections.

  2. Surface Facial Electromyography Reactions to Light-Relevant and Season-Relevant Stimuli in Seasonal Affective Disorder


    psychophysiological responding in the nonseasonal depression literature (e.g., Cacioppo, Bush, & Tassinary, 1992; Greden, Genero , Price, Feinberg...with Schwartz et al. (1978) and Carney et al. (1981), Greden, Price, Genero , Feinberg, and Levine (1984) found that higher baseline levels of facial...York: Academic Press. Greden, J. F., Price, H. L., Genero , N., Feinberg, M., & Levine, S. (1984). Facial EMG activity levels predict treatment

  3. Effect of heterogeneous aqueous reactions on the secondary formation of inorganic aerosols during haze events

    Quan, Jiannong; Liu, Quan; Li, Xia; Gao, Yang; Jia, Xingcan; Sheng, Jiujiang; Liu, Yangang


    The effect of heterogeneous aqueous reactions on the secondary formation of inorganic aerosols during haze events was investigated by analysis of comprehensive measurements of aerosol composition and concentrations [e.g., particular matters (PM2.5), nitrate (NO3), sulfate (SO4), ammonium (NH4)], gas-phase precursors [e.g., nitrogen oxides (NOx), sulfur dioxide (SO2), and ozone (O3)], and relevant meteorological parameters [e.g., visibility and relative humidity (RH)]. The measurements were conducted in Beijing, China from Sep. 07, 2012 to Jan. 16, 2013. The results show that the conversion ratios of N from NOx to nitrate (Nratio) and S from SO2 to sulfate (Sratio) both significantly increased in haze events, suggesting enhanced conversions from NOx and SO2 to their corresponding particle phases in the late haze period. Further analysis shows that Nratio and Sratio increased with increasing RH, with Nratio and Sratio being only 0.04 and 0.03, respectively, when RH aqueous reactions, because solar radiation and thus the photochemical capacity are reduced by the increases in aerosols and RH. This point was further affirmed by the relationships of Nratio and Sratio to O3: the conversion ratios increase with decreasing O3 concentration when O3 concentration is lower than aqueous reactions likely changed aerosols and their precursors during the haze events: in the beginning of haze events, the precursor gases accumulated quickly due to high emission and low reaction rate; the occurrence of heterogeneous aqueous reactions in the late haze period, together with the accumulated high concentrations of precursor gases such as SO2 and NOx, accelerated the formation of secondary inorganic aerosols, and led to rapid increase of the PM2.5 concentration.

  4. Correlation between the Female Apheresis Platelet Donors′ Sodium Citrate Toxic Reaction and the Anticoagulant Concentration%女性机采血小板献血者枸橼酸钠中毒与抗凝剂比例的关系



    Objective To investigate the relationship of the female apheresis platelet donors' sodium citrate toxic reaction and the anticoagulant concentration. Methods 181 cases of female platelet donors at blood center were randomly divided into group A of 80 cases and group B. Of 101 cases, sodium citrate poisoning cases in anticoagulant/blood ratio of 1:10( group A)and 1: 11( group B )female platelet donors were observed and compared. Results When the ratio of anticoagulant and whole blood was 1=11,1.98% of the female donors of group B had sodium citrate toxicity reactions, which was significantly lower than group A with the ratio of anticoagulant and whole blood 1: 10. The difference of incidence of sodium toxic reactions was statistically significant( P <0. 05 ). Conclusion Women in Jiangsu Province generally have smaller body weight,the use of appropriate anticoagulant concentration( the ratio of anticoagulant and whole blood 1 : 11 )can significantly reduce the incidence of sodium citrate toxic reaction of the female apheresis platelet donors, which has important application value.%目的 探讨女性机采血小板献血者枸橼酸钠中毒与抗凝剂比例的关系.方法 对来血液中心进行机采血小板的181例女性献血者随机分为A组80例,B组101例.对比观察抗凝剂与全血比例为1:10(A组)和1:11时(B组)女性机采血小板献血者发生枸橼酸钠中毒的情况.结果 抗凝剂与全血比例为1:11的B组女性献血者枸橼酸钠中毒反应发生率为1.98%,明显低于抗凝剂与全血比例为1:10的A组女性献血者,比较差异有统计学意义(P<0.05).结论 江苏地区女性体质量普遍较轻,采用抗凝剂与全血比例为1:11可明显改善女性机采血小板献血者枸橼酸钠中毒反应的发生率,具有重要的应用价值.

  5. The Need for Culturally Relevant Dance Education

    McCarthy-Brown, Nyama


    There is a need for culturally relevant teaching in dance education. Many dance teachers have heard the buzz words "culturally relevant teaching methods." Yet these dance educators acknowledge that the "dance culture" is not always synonymous with "culturally relevant." This paper examines the issue of culturally relevant teaching methods in dance…

  6. Combustion kinetics and reaction pathways

    Klemm, R.B.; Sutherland, J.W. [Brookhaven National Laboratory, Upton, NY (United States)


    This project is focused on the fundamental chemistry of combustion. The overall objectives are to determine rate constants for elementary reactions and to elucidate the pathways of multichannel reactions. A multitechnique approach that features three independent experiments provides unique capabilities in performing reliable kinetic measurements over an exceptionally wide range in temperature, 300 to 2500 K. Recent kinetic work has focused on experimental studies and theoretical calculations of the methane dissociation system (CH{sub 4} + Ar {yields} CH{sub 3} + H + Ar and H + CH{sub 4} {yields} CH{sub 3} + H{sub 2}). Additionally, a discharge flow-photoionization mass spectrometer (DF-PIMS) experiment is used to determine branching fractions for multichannel reactions and to measure ionization thresholds of free radicals. Thus, these photoionization experiments generate data that are relevant to both reaction pathways studies (reaction dynamics) and fundamental thermochemical research. Two distinct advantages of performing PIMS with high intensity, tunable vacuum ultraviolet light at the National Synchrotron Light Source are high detection sensitivity and exceptional selectivity in monitoring radical species.

  7. Relevance of latex aeroallergen for healthcare workers

    X. Baur


    Full Text Available The dispersion of latex allergen bound on glove powder has been shown to be of clinical importance to latex-sensitized medical staff and patients. To investigate whether latex aeroallergen is associated with the development of latex allergic reactions in health care workers, air samples were collected in 33 hospital rooms and two physicians' offices. Concentrations of latex allergens in the samples were determined by a competitive inhibition immunoassay and related to reported hypersensitivity reactions and to specific IgE results of 111 staff members engaged in these rooms. Latex aeroallergen (up to 205 ng/m3 could be detected in all rooms where powdered latex gloves were used and ventilation systems were not installed. Conjunctivitis (n=10, rhinitis (n=12 and dyspnea (n=4 were reported exclusively by employees working in such contaminated rooms. Also workers with latex-specific IgE antibodies (n=l 7 were found only in these rooms. Urticaria in personnel (n=26 was reported in rooms with and without detectable allergen load. All symptoms were significantly associated with latex-specific IgE antibodies. Our results demonstrate that immediate-type sensitization and allergic symptoms are associated with detectable latex aeroallergen.

  8. Kinetic Investigations on the Leaching of Niobium from a Low-Grade Niobium-Tantalum Ore by Concentrated KOH Solution

    周宏明; 郑诗礼; 张懿


    The leaching kinetics of niobium from a low-gr~te niobium-tantalum ore by concentrated KOH solution under atmospheric pressure has been studied. Significant effects of reaction temperature, KOH concentration,stirring speed, particle size and mass ratio of alkali-to-ore on the dissolution rate of niobium were examined. The experimental data of the leaching rates and the observed effects of the relevant operating variables were well interpreted with a shrinking core model under diffusion control. By using the Arrhenius expression, the apparent activation energy for the dissolution of niobium was evaluated. Finally, on the base of the shrinking core model, the rate equation was established.

  9. Ancient "Observatories" - A Relevant Concept?

    Belmonte, Juan Antonio

    It is quite common, when reading popular books on astronomy, to see a place referred to as "the oldest observatory in the world". In addition, numerous books on archaeoastronomy, of various levels of quality, frequently refer to the existence of "prehistoric" or "ancient" observatories when describing or citing monuments that were certainly not built with the primary purpose of observing the skies. Internet sources are also guilty of this practice. In this chapter, the different meanings of the word observatory will be analyzed, looking at how their significances can be easily confused or even interchanged. The proclaimed "ancient observatories" are a typical result of this situation. Finally, the relevance of the concept of the ancient observatory will be evaluated.

  10. Apparent Rate Constant for Diffusion-Controlled Three molecular (catalytic) reaction

    Burlatsky, S. F.; Moreau, M


    We present simple explicit estimates for the apparent reaction rate constant for three molecular reactions, which are important in catalysis. For small concentrations and $d> 1$, the apparent reaction rate constant depends only on the diffusion coefficients and sizes of the particles. For small concentrations and $d\\le 1$, it is also time -- dependent. For large concentrations, it gains the dependence on concentrations.

  11. Catalysis of Photochemical Reactions.

    Albini, A.


    Offers a classification system of catalytic effects in photochemical reactions, contrasting characteristic properties of photochemical and thermal reactions. Discusses catalysis and sensitization, examples of catalyzed reactions of excepted states, complexing ground state substrates, and catalysis of primary photoproducts. (JM)

  12. Variance-corrected Michaelis-Menten equation predicts transient rates of single-enzyme reactions and response times in bacterial gene-regulation.

    Pulkkinen, Otto; Metzler, Ralf


    Many chemical reactions in biological cells occur at very low concentrations of constituent molecules. Thus, transcriptional gene-regulation is often controlled by poorly expressed transcription-factors, such as E.coli lac repressor with few tens of copies. Here we study the effects of inherent concentration fluctuations of substrate-molecules on the seminal Michaelis-Menten scheme of biochemical reactions. We present a universal correction to the Michaelis-Menten equation for the reaction-rates. The relevance and validity of this correction for enzymatic reactions and intracellular gene-regulation is demonstrated. Our analytical theory and simulation results confirm that the proposed variance-corrected Michaelis-Menten equation predicts the rate of reactions with remarkable accuracy even in the presence of large non-equilibrium concentration fluctuations. The major advantage of our approach is that it involves only the mean and variance of the substrate-molecule concentration. Our theory is therefore accessible to experiments and not specific to the exact source of the concentration fluctuations.

  13. Inactivation of the antibacterial and cytotoxic properties of silver ions by biologically relevant compounds.

    Geraldine Mulley

    Full Text Available There has been a recent surge in the use of silver as an antimicrobial agent in a wide range of domestic and clinical products, intended to prevent or treat bacterial infections and reduce bacterial colonization of surfaces. It has been reported that the antibacterial and cytotoxic properties of silver are affected by the assay conditions, particularly the type of growth media used in vitro. The toxicity of Ag+ to bacterial cells is comparable to that of human cells. We demonstrate that biologically relevant compounds such as glutathione, cysteine and human blood components significantly reduce the toxicity of silver ions to clinically relevant pathogenic bacteria and primary human dermal fibroblasts (skin cells. Bacteria are able to grow normally in the presence of silver nitrate at >20-fold the minimum inhibitory concentration (MIC if Ag+ and thiols are added in a 1:1 ratio because the reaction of Ag+ with extracellular thiols prevents silver ions from interacting with cells. Extracellular thiols and human serum also significantly reduce the antimicrobial activity of silver wound dressings Aquacel-Ag (Convatec and Acticoat (Smith & Nephew to Staphylococcus aureus, Pseudomonas aeruginosa and Escherichia coli in vitro. These results have important implications for the deployment of silver as an antimicrobial agent in environments exposed to biological tissue or secretions. Significant amounts of money and effort have been directed at the development of silver-coated medical devices (e.g. dressings, catheters, implants. We believe our findings are essential for the effective design and testing of antimicrobial silver coatings.

  14. [Allergic reactions to transfusion].

    Hergon, E; Paitre, M L; Coeffic, B; Piard, N; Bidet, J M


    Frequent allergic reactions following transfusion are observed. Usually, they are benign but sometimes we observe severe allergic reactions. Adverse reactions may be brought about by least two mechanisms. First, immediate-type hypersensibility reactions due to IgE. Secondly, anaphylactic-type reactions due to interaction between transfused IgA and class specific anti IgA in the recipient's plasma. They are characterized by their severest form (anaphylactic shock). The frequency of severe reactions following the transfusion blood plasma is very low. These transfusion reactions are complement-mediated and kinins-mediated. Prevention of allergic reactions is necessary among blood donors and recipients.

  15. Evaluation of eicosanoid concentrations in stored units of canine packed red blood cells.

    Blake, Rachel R; Lee, Jung Hwa; Ross, Matt K; Archer, Todd M; Wills, Robert W; Mackin, Andrew J; Thomason, John M


    OBJECTIVE To evaluate eicosanoid concentrations in freshly prepared canine packed RBCs (PRBCs) and to assess changes in eicosanoid concentrations in PRBC units over time during storage and under transfusion conditions. DESIGN Prospective study. SAMPLE 25 plasma samples from 14 healthy Greyhounds. PROCEDURES Plasma samples were obtained during PRBC preparation (donation samples), and the PRBC units were then stored at 4°C until used for transfusion (≤ 21 days later; n = 17) or mock transfusion if expired (22 to 24 days later; 8). Immediately prior to use, 100 mL of saline (0.9% NaCl) solution was added to each unit and a pretransfusion sample was collected. A posttransfusion sample was collected after transfusion or mock transfusion. Concentrations of arachidonic acid, prostaglandin (PG) F2α, PGE2, PGD2, thromboxane B2, 6-keto-PGF1α, and leukotriene B4 were measured by liquid chromatography-mass spectrometry and analyzed statistically. RESULTS Median arachidonic acid concentration was significantly decreased in posttransfusion samples, compared with the concentration in donation samples. Median PGF2α, 6-keto-PGF1α, and leukotriene B4 concentrations were significantly increased in pretransfusion samples, compared with those in donation samples. Median PGF2α, thromboxane B2, and 6-keto-PGF1α concentrations were significantly increased in posttransfusion samples, compared with those in pretransfusion samples. Duration of PRBC storage had significant associations with pretransfusion and posttransfusion arachidonic acid and thromboxane B2 concentrations. CONCLUSIONS AND CLINICAL RELEVANCE Concentrations of several proinflammatory eicosanoids increased in PRBC units during storage, transfusion, or both. Accumulation of these products could potentially contribute to adverse transfusion reactions, and investigation of the potential association between eicosanoid concentrations in PRBCs and the incidence of transfusion reactions in dogs is warranted.

  16. Rapid magnetic removal of aqueous heavy metals and their relevant mechanisms using nanoscale zero valent iron (nZVI) particles.

    Huang, Pengpeng; Ye, Zhengfang; Xie, Wuming; Chen, Qi; Li, Jing; Xu, Zhencheng; Yao, Maosheng


    Much work is devoted to heavy metal sorption, reduction and relevant mechanisms by nanoscale zero valent iron (nZVI) particle, but fewer studies utilize its magnetic properties in aqueous metal removals. Here, we have investigated the use of nZVI particles both electrosprayed (E-nZVI) and non-electrosprayed (NE-nZVI) with different concentration levels (0.186-1.86 mg/mL) in removing aqueous Cd(II), Cr(IV), and Pb(II) through the magnetic separation means. The effects of the reaction time (5-20 min) and magnetic treatment time (1-30 min) on relevant magnetic removal efficiencies were studied. Metal ion concentration was analyzed using inductively coupled plasma (ICP), and the magnetically obtained metal-nZVI mixtures were further analyzed using X-ray photoelectron spectroscopy (XPS). Results showed that the magnetic removal efficiencies of heavy metals varied with the metal species, nZVI loading, reaction and magnetic separation time. In most cases, use of 1.5 mg/mL E-nZVI or NE-nZVI resulted in removal efficiencies of more than 80% for Pb(II), Cd(II), and Cr(IV). Increasing the magnetic treatment time from 1 to 20 min was shown to lead to ≈ 20% increase in Pb(II) removal efficiency, but no improvements for Cd(II) and Cr(IV). In contrast, increasing the reaction time decreased the Pb(II) removal efficiency, yet no effects observed for Cd(II) and Cr(IV). In general, 1 min reaction and 5 min magnetic treatment were found sufficient to achieve considerable heavy metal removals. For comparable efficiencies, use of magnetic method could significantly reduce nZVI loading. XPS analysis results indicated that atomic percentages of O 1s, Fe 2p, Cd 3d, Pb 4f and Cr 2p varied with metal exposures. Different from Cd(II) and Cr(IV), aqueous iron ions might be possibly present when treating Pb(II). This study demonstrated a rapid heavy metal removal method using the magnetic property of nZVI particles, while contributing to understanding of the relevant removal mechanisms.

  17. Vygotsky's Crisis: Argument, context, relevance.

    Hyman, Ludmila


    Vygotsky's The Historical Significance of the Crisis in Psychology (1926-1927) is an important text in the history and philosophy of psychology that has only become available to scholars in 1982 in Russian, and in 1997 in English. The goal of this paper is to introduce Vygotsky's conception of psychology to a wider audience. I argue that Vygotsky's argument about the "crisis" in psychology and its resolution can be fully understood only in the context of his social and political thinking. Vygotsky shared the enthusiasm, widespread among Russian leftist intelligentsia in the 1920s, that Soviet society had launched an unprecedented social experiment: The socialist revolution opened the way for establishing social conditions that would let the individual flourish. For Vygotsky, this meant that "a new man" of the future would become "the first and only species in biology that would create itself." He envisioned psychology as a science that would serve this humanist teleology. I propose that The Crisis is relevant today insofar as it helps us define a fundamental problem: How can we systematically account for the development of knowledge in psychology? I evaluate how Vygotsky addresses this problem as a historian of the crisis. Copyright © 2011 Elsevier Ltd. All rights reserved.

  18. Combined online spectroscopic, calorimetric, and chemometric analysis: reaction enthalpy determinations in single and parallel reactions.

    Tjahjono, Martin; Widjaja, Effendi; Garland, Marc


    Calorimetry and signal processing: Vibrational spectroscopies, heat-flow microcalorimetry, and multivariate analysis are combined to decouple the reaction enthalpies of parallel reactions [picture: see text]. This methodology allows the evaluation of reaction enthalpy from complex systems without recourse to conventional kinetic modeling. Simultaneous in situ/online spectroscopy and heat-flow measurements as well as multivariate analyses are performed, apparently for the first time, to determine heats of reaction for single and parallel reactions. Two different vibrational spectroscopy techniques, namely Raman and FTIR spectroscopy, are used in conjunction with flow-through TAM III microcalorimetry. With respect to the spectroscopic analysis, the reaction spectra are first analyzed to determine the pure-component spectra and the corresponding concentrations without recourse to external calibration. With respect to the calorimetric analysis, a soft modeling approach is employed to determine the heats of reaction without recourse to any conventional kinetic models. This combined approach is implemented to determine the extents of reaction as well as the corresponding heats of reaction at 298.15 K and 0.1 MPa for a) the hydrolysis of acetic anhydride (single reaction) and b) the hydrolysis of methyl paraben and ethyl paraben in alkaline solution (both single and parallel reactions). In the latter case, the heat-flow contributions from the two simultaneous reactions are successfully decoupled. Taken together, these results demonstrate proof of concept for the present approach. The newly developed methodology appears to be quite general and particularly useful for investigating complex reaction systems. This is particularly true for multiple simultaneous reactions and reactions where the detailed kinetic expressions are not available, or cannot be easily determined. The use of extents of reaction is also very helpful where there is high variability in reaction rates

  19. Reaction dynamics in polyatomic molecular systems

    Miller, W.H. [Lawrence Berkeley Laboratory, CA (United States)


    The goal of this program is the development of theoretical methods and models for describing the dynamics of chemical reactions, with specific interest for application to polyatomic molecular systems of special interest and relevance. There is interest in developing the most rigorous possible theoretical approaches and also in more approximate treatments that are more readily applicable to complex systems.

  20. Effect of reactions in small eddies on biomass gasification with eddy dissipation concept - Sub-grid scale reaction model.

    Chen, Juhui; Yin, Weijie; Wang, Shuai; Meng, Cheng; Li, Jiuru; Qin, Bai; Yu, Guangbin


    Large-eddy simulation (LES) approach is used for gas turbulence, and eddy dissipation concept (EDC)-sub-grid scale (SGS) reaction model is employed for reactions in small eddies. The simulated gas molar fractions are in better agreement with experimental data with EDC-SGS reaction model. The effect of reactions in small eddies on biomass gasification is emphatically analyzed with EDC-SGS reaction model. The distributions of the SGS reaction rates which represent the reactions in small eddies with particles concentration and temperature are analyzed. The distributions of SGS reaction rates have the similar trend with those of total reactions rates and the values account for about 15% of the total reactions rates. The heterogeneous reaction rates with EDC-SGS reaction model are also improved during the biomass gasification process in bubbling fluidized bed.

  1. The reaction index and positivity ratio revisited

    Andersen, Klaus Ejner; Andersen, Flemming


    BACKGROUND AND OBJECTIVES: Assessing the quality of patch test preparations continues to be a challenge. 2 parameters, the reaction index (RI) and positivity ratio (PR), have been proposed as quality indicators by the Information Network of Departments of Dermatology (IVDK). The value of these st......BACKGROUND AND OBJECTIVES: Assessing the quality of patch test preparations continues to be a challenge. 2 parameters, the reaction index (RI) and positivity ratio (PR), have been proposed as quality indicators by the Information Network of Departments of Dermatology (IVDK). The value...... of the IVDK and our department. Calculation of RI's and PR's for patch test allergens is of limited value as a measure of quality of the patch test materials, because it predominantly reflects differences in scoring and reading of patch test reactions. Further, questionable reactions (+?) may be clinically...... relevant and very important for the individual patient. Focus on standardization of patch test materials, patch test technique, and reading of patch test reactions is mandatory....

  2. Mechanisms of inorganic and organometallic reactions

    The purpose of this series is to provide a continuing critical review of the literature concerned with mechanistic aspects of inorganic and organo­ metallic reactions in solution, with coverage being complete in each volume. The papers discussed are selected on the basis of relevance to the elucidation of reaction mechanisms and many include results of a nonkinetic nature when useful mechanistic information can be deduced. The period of literature covered by this volume is July 1982 through December 1983, and in some instances papers not available for inclusion in the previous volume are also included. Numerical results are usually reported in the units used by the original authors, except where data from different papers are com­ pared and conversion to common units is necessary. As in previous volumes material included covers the major areas of redox processes, reactions of the nonmetallic elements, reaction of inert and labile metal complexes and the reactions of organometallic compounds. While m...

  3. Ambient sesquiterpene concentration and its link to air ion measurements

    B. Bonn


    Full Text Available Ambient air ion size distributions have been measured continuously at the Finnish boreal forest site in Hyytiälä since spring 2003. In general, these measurements show a maximum of air ions below 1.0 nm in diameter. But this physical characterization does not provide any information about the ion's chemical composition, which is one key question regarding the explanation of nucleation events observed. In this study we propose a link of the observed maximum of negative air ions between 0.56 and 0.75 nm to the so-called stabilised Criegee biradical, formed in the reaction of biogenic sesquiterpenes with ozone and predominantly destroyed by its reaction with ambient water vapour. Calculations of the electron and proton affinities of 120 kJ mol−1 (1.24 eV and of 960 kJ mol−1 support this link. Other possible candidates such as sulphuric acid derived clusters are unable to explain the observations made. By using this approach, we are able to calculate the ambient concentration of sesquiterpenes at the air ion instrument inlet with a high time resolution on the daily and seasonal scale. The estimated concentration is found to reveal the same seasonal pattern as emission measurements conducted at shoot level. As expected for biogenic VOCs, the concentration is obtained highest during summer (maximum values of about 100 pptv and smallest during winter (minimum less than 1 pptv. Because of the sesquiterpenes high reactivity and its low ambient concentrations, this approach can be a first step in understanding their emission and their impact on atmospheric chemistry in more detail. The findings presented are highly relevant for emission budgets too, since boreal forests are extended over large areas of the globe.

  4. Ambient sesquiterpene concentration and its link to air ion measurements

    B. Bonn


    Full Text Available Ambient air ion size distributions have been measured continuously at the Finnish boreal forest site in Hyytiälä since spring 2003. In general, these measurements show a maximum of air ions below 1.0 nm in diameter. But this physical characterization does not provide any information about the ion's chemical composition, which is one key question regarding the explanation of nucleation events observed. In this study we propose a link of the observed maximum of negative air ions between 0.56 and 0.75 nm to the so-called stabilised Criegee biradical, formed in the reaction of biogenic sesquiterpenes with ozone and predominantly destroyed by its reaction with ambient water vapour. Calculations of the electron and proton affinities of 120 kJ mol−1 (1.24 eV and of 960 kJ mol−1 support this link. Other possible candidates such as sulphuric acid derived clusters are unable to explain the observations made. By using this approach, we are able to calculate the ambient concentration of sesquiterpenes at the air ion instrument inlet with a high time resolution on the daily and seasonal scale. The estimated concentration is found to reveal the same seasonal pattern as emission measurements conducted at shoot level. As expected for biogenic VOCs, the concentration is obtained highest during summer (maximum values of about 100 pptv and smallest during winter (minimum less than 1 pptv. Because of the sesquiterpenes high reactivity and its low ambient concentrations, this approach can be a first step in understanding their emission and their impact on atmospheric chemistry in more detail. The findings presented are highly relevant for emission budgets too, since boreal forests are extended over large areas of the globe.

  5. Does relevance matter in academic policy research?

    Dredge, Dianne


    A reflection on whether relevance matters in tourism policy research. A debate among tourism scholars.......A reflection on whether relevance matters in tourism policy research. A debate among tourism scholars....

  6. Statistical significance versus clinical relevance.

    van Rijn, Marieke H C; Bech, Anneke; Bouyer, Jean; van den Brand, Jan A J G


    In March this year, the American Statistical Association (ASA) posted a statement on the correct use of P-values, in response to a growing concern that the P-value is commonly misused and misinterpreted. We aim to translate these warnings given by the ASA into a language more easily understood by clinicians and researchers without a deep background in statistics. Moreover, we intend to illustrate the limitations of P-values, even when used and interpreted correctly, and bring more attention to the clinical relevance of study findings using two recently reported studies as examples. We argue that P-values are often misinterpreted. A common mistake is saying that P < 0.05 means that the null hypothesis is false, and P ≥0.05 means that the null hypothesis is true. The correct interpretation of a P-value of 0.05 is that if the null hypothesis were indeed true, a similar or more extreme result would occur 5% of the times upon repeating the study in a similar sample. In other words, the P-value informs about the likelihood of the data given the null hypothesis and not the other way around. A possible alternative related to the P-value is the confidence interval (CI). It provides more information on the magnitude of an effect and the imprecision with which that effect was estimated. However, there is no magic bullet to replace P-values and stop erroneous interpretation of scientific results. Scientists and readers alike should make themselves familiar with the correct, nuanced interpretation of statistical tests, P-values and CIs. © The Author 2017. Published by Oxford University Press on behalf of ERA-EDTA. All rights reserved.

  7. Microbial reactions in coal and coal relevant structures. Part project: fungal and enzymatic depolarisation of brown coal for the production of low-molecular compounds. Interim report; Mikrobielle Umsetzung an Kohle und kohlenrelevanten Strukturen. Teilvorhaben: Pilzliche und enzymatische Depolymerisation von Braunkohle zur Gewinnung niedermolekularer Verbindungen. Zwischenbericht (Berichtszeitraum 01.01.1998 - 31.12.1998)

    Ziegenhagen, D.; Bublitz, F.; Sorge, S.; Ullrich, R.; Hofrichter, M.; Fritsche, W.


    The present research project involved a study of the depolymerisation of brown coal constituents. The purpose of the depolymerisation experiments, which were carried out with fungi as well as their (acellular) enzymes, was to obtain products with a potential market value. Research focussed on one of the key enzymes of lignocellulose degradation, namely manganese (II) peroxidase (MnP). The effects of this enzyme on the depolymerisation of brown coal was studied in detail in acellular systems. The insights gained in this way then served as a basis for optimising the fungal and enzymatic depolymerisation processes for maximum yields of low-molecular products. The experiments carried out during the period under review were oriented to finding new types of lignolytically active organisms, isolating lignolytic enzymes and immobilising them on natural support materials, and further examining the action spectrum of MnP. Different model substrates were used in order to gain information on what bond types are MnP-cleavable and on possible reaction products. Substrates were either fixed to silica gel as support material or used without support material. The idea of using substrates fixed to support materials was motivated by the need to distinguish between intracellular and extracellular reactions involving the fungal mycelium. [Deutsch] Im Rahmen des Forschungsvorhabens wird die Depolymerisation von Braunkohle-Bestandteilen untersucht. Ziel der sowohl mit Pilzorganismen als auch mit deren Enzymen (zellfrei) durchgefuehrten Depolymerisationsversuche ist die Gewinnung von Produkten mit potentiellem Werkstoffcharakter. Im Mittelpunkt der Forschung steht eines der Schluesselenzyme des Ligninozellulose-Abbaus: Die Mangan(II)-Peroxidase (MnP). Die Wirkung dieses Enzyms bei der Depolymerisation von Braunkohle (Bk) in zellfreien Systemen wird weitergehend untersucht. Auf Grundlage der gewonnenen Erkenntnisse werden die pilzlichen und enzymatischen Depolymerisationsprozesse so


    Peters, Catherine A [Princeton University


    This project addressed the scaling of geochemical reactions to core and field scales, and the interrelationship between reaction rates and flow in porous media. We targeted reactive transport problems relevant to the Hanford site specifically the reaction of highly caustic, radioactive waste solutions with subsurface sediments, and the immobilization of 90Sr and 129I through mineral incorporation and passive flow blockage, respectively. We addressed the correlation of results for pore-scale fluid-soil interaction with field-scale fluid flow, with the specific goals of (i) predicting attenuation of radionuclide concentration; (ii) estimating changes in flow rates through changes of soil permeabilities; and (iii) estimating effective reaction rates. In supplemental work, we also simulated reactive transport systems relevant to geologic carbon sequestration. As a whole, this research generated a better understanding of reactive transport in porous media, and resulted in more accurate methods for reaction rate upscaling and improved prediction of permeability evolution. These scientific advancements will ultimately lead to better tools for management and remediation of DOE legacy waste problems.

  9. The Personal Relevance of the Social Studies.

    VanSickle, Ronald L.


    Conceptualizes a personal-relevance framework derived from Ronald L. VanSickle's five areas of life integrated with four general motivating goals from Abraham Maslow's hierarchy of needs and Richard and Patricia Schmuck's social motivation theory. Illustrates ways to apply the personal relevance framework to make social studies more relevant to…

  10. Science and the struggle for relevance

    Hessels, L.K.


    This thesis deals with struggles for relevance of university researchers, their efforts to make their work correspond with ruling standards of relevance and to influence these standards. Its general research question is: How to understand changes in the struggle for relevance of Dutch academic resea

  11. Relevance Measures Using Geographic Scopes and Types

    Andogah, Geoffrey; Bouma, Gosse; Peters, C; Jikoun,; Mandl, T; Muller, H; Oard, DW; Penas, A; Petras,; Santos, D


    This paper proposes two kinds of relevance measures to rank documents by geographic restriction: scope-based and type-based. The non-geographic and geographic relevance scores are combined using a weighted harmonic mean. The proposed relevance measures and weighting schemes are evaluated on GeoCLEF

  12. The Personal Relevance of the Social Studies.

    VanSickle, Ronald L.


    Conceptualizes a personal-relevance framework derived from Ronald L. VanSickle's five areas of life integrated with four general motivating goals from Abraham Maslow's hierarchy of needs and Richard and Patricia Schmuck's social motivation theory. Illustrates ways to apply the personal relevance framework to make social studies more relevant to…

  13. Science and the struggle for relevance

    Hessels, L.K.|info:eu-repo/dai/nl/304832863


    This thesis deals with struggles for relevance of university researchers, their efforts to make their work correspond with ruling standards of relevance and to influence these standards. Its general research question is: How to understand changes in the struggle for relevance of Dutch academic

  14. Enhanced electrocatalytic CO2 reduction via field-induced reagent concentration

    Liu, Min; Pang, Yuanjie; Zhang, Bo; de Luna, Phil; Voznyy, Oleksandr; Xu, Jixian; Zheng, Xueli; Dinh, Cao Thang; Fan, Fengjia; Cao, Changhong; de Arquer, F. Pelayo García; Safaei, Tina Saberi; Mepham, Adam; Klinkova, Anna; Kumacheva, Eugenia; Filleter, Tobin; Sinton, David; Kelley, Shana O.; Sargent, Edward H.


    Electrochemical reduction of carbon dioxide (CO2) to carbon monoxide (CO) is the first step in the synthesis of more complex carbon-based fuels and feedstocks using renewable electricity. Unfortunately, the reaction suffers from slow kinetics owing to the low local concentration of CO2 surrounding typical CO2 reduction reaction catalysts. Alkali metal cations are known to overcome this limitation through non-covalent interactions with adsorbed reagent species, but the effect is restricted by the solubility of relevant salts. Large applied electrode potentials can also enhance CO2 adsorption, but this comes at the cost of increased hydrogen (H2) evolution. Here we report that nanostructured electrodes produce, at low applied overpotentials, local high electric fields that concentrate electrolyte cations, which in turn leads to a high local concentration of CO2 close to the active CO2 reduction reaction surface. Simulations reveal tenfold higher electric fields associated with metallic nanometre-sized tips compared to quasi-planar electrode regions, and measurements using gold nanoneedles confirm a field-induced reagent concentration that enables the CO2 reduction reaction to proceed with a geometric current density for CO of 22 milliamperes per square centimetre at -0.35 volts (overpotential of 0.24 volts). This performance surpasses by an order of magnitude the performance of the best gold nanorods, nanoparticles and oxide-derived noble metal catalysts. Similarly designed palladium nanoneedle electrocatalysts produce formate with a Faradaic efficiency of more than 90 per cent and an unprecedented geometric current density for formate of 10 milliamperes per square centimetre at -0.2 volts, demonstrating the wider applicability of the field-induced reagent concentration concept.

  15. Enhanced electrocatalytic CO2 reduction via field-induced reagent concentration.

    Liu, Min; Pang, Yuanjie; Zhang, Bo; De Luna, Phil; Voznyy, Oleksandr; Xu, Jixian; Zheng, Xueli; Dinh, Cao Thang; Fan, Fengjia; Cao, Changhong; de Arquer, F Pelayo García; Safaei, Tina Saberi; Mepham, Adam; Klinkova, Anna; Kumacheva, Eugenia; Filleter, Tobin; Sinton, David; Kelley, Shana O; Sargent, Edward H


    Electrochemical reduction of carbon dioxide (CO2) to carbon monoxide (CO) is the first step in the synthesis of more complex carbon-based fuels and feedstocks using renewable electricity. Unfortunately, the reaction suffers from slow kinetics owing to the low local concentration of CO2 surrounding typical CO2 reduction reaction catalysts. Alkali metal cations are known to overcome this limitation through non-covalent interactions with adsorbed reagent species, but the effect is restricted by the solubility of relevant salts. Large applied electrode potentials can also enhance CO2 adsorption, but this comes at the cost of increased hydrogen (H2) evolution. Here we report that nanostructured electrodes produce, at low applied overpotentials, local high electric fields that concentrate electrolyte cations, which in turn leads to a high local concentration of CO2 close to the active CO2 reduction reaction surface. Simulations reveal tenfold higher electric fields associated with metallic nanometre-sized tips compared to quasi-planar electrode regions, and measurements using gold nanoneedles confirm a field-induced reagent concentration that enables the CO2 reduction reaction to proceed with a geometric current density for CO of 22 milliamperes per square centimetre at -0.35 volts (overpotential of 0.24 volts). This performance surpasses by an order of magnitude the performance of the best gold nanorods, nanoparticles and oxide-derived noble metal catalysts. Similarly designed palladium nanoneedle electrocatalysts produce formate with a Faradaic efficiency of more than 90 per cent and an unprecedented geometric current density for formate of 10 milliamperes per square centimetre at -0.2 volts, demonstrating the wider applicability of the field-induced reagent concentration concept.

  16. Diverse microbial species survive high ammonia concentrations

    Kelly, Laura C.; Cockell, Charles S.; Summers, Stephen


    Planetary protection regulations are in place to control the contamination of planets and moons with terrestrial micro-organisms in order to avoid jeopardizing future scientific investigations relating to the search for life. One environmental chemical factor of relevance in extraterrestrial environments, specifically in the moons of the outer solar system, is ammonia (NH3). Ammonia is known to be highly toxic to micro-organisms and may disrupt proton motive force, interfere with cellular redox reactions or cause an increase of cell pH. To test the survival potential of terrestrial micro-organisms exposed to such cold, ammonia-rich environments, and to judge whether current planetary protection regulations are sufficient, soil samples were exposed to concentrations of NH3 from 5 to 35% (v/v) at -80°C and room temperature for periods up to 11 months. Following exposure to 35% NH3, diverse spore-forming taxa survived, including representatives of the Firmicutes (Bacillus, Sporosarcina, Viridibacillus, Paenibacillus, Staphylococcus and Brevibacillus) and Actinobacteria (Streptomyces). Non-spore forming organisms also survived, including Proteobacteria (Pseudomonas) and Actinobacteria (Arthrobacter) that are known to have environmentally resistant resting states. Clostridium spp. were isolated from the exposed soil under anaerobic culture. High NH3 was shown to cause a reduction in viability of spores over time, but spore morphology was not visibly altered. In addition to its implications for planetary protection, these data show that a large number of bacteria, potentially including spore-forming pathogens, but also environmentally resistant non-spore-formers, can survive high ammonia concentrations.

  17. Mechanistic study of secondary organic aerosol components formed from nucleophilic addition reactions of methacrylic acid epoxide

    A. W. Birdsall


    Full Text Available Recently, methacrylic acid epoxide (MAE has been proposed as a precursor to an important class of isoprene-derived compounds found in secondary organic aerosol (SOA: 2-methylglyceric acid (2-MG and a set of oligomers, nitric acid esters and sulfuric acid esters related to 2-MG. However, the specific chemical mechanisms by which MAE could form these compounds have not been previously studied. In order to determine the relevance of these processes to atmospheric aerosol, MAE and 2-MG have been synthesized and a series of bulk solution-phase experiments aimed at studying the reactivity of MAE using nuclear magnetic resonance (NMR spectroscopy have been performed. The present results indicate that the acid-catalyzed MAE reaction is more than 600 times slower than a similar reaction of an important isoprene-derived epoxide, but is still expected to be kinetically feasible in the atmosphere on more acidic SOA. The specific mechanism by which MAE leads to oligomers was identified, and the reactions of MAE with a number of atmospherically relevant nucleophiles were also investigated. Because the nucleophilic strengths of water, sulfate, alcohols (including 2-MG, and acids (including MAE and 2-MG in their reactions with MAE were found to be of a similar magnitude, it is expected that a diverse variety of MAE + nucleophile product species may be formed on ambient SOA. Thus, the results indicate that epoxide chain reaction oligomerization will be limited by the presence of high concentrations of non-epoxide nucleophiles (such as water; this finding is consistent with previous environmental chamber investigations of the relative humidity-dependence of 2-MG-derived oligomerization processes and suggests that extensive oligomerization may not be likely on ambient SOA because of other competitive MAE reaction mechanisms.

  18. Atom addition reactions in interstellar ice analogues

    Linnartz, Harold; Fedoseev, Gleb


    This review paper summarizes the state-of-the-art in laboratory based interstellar ice chemistry. The focus is on atom addition reactions, illustrating how water, carbon dioxide and methanol can form in the solid state at astronomically relevant temperatures, and also the formation of more complex species such as hydroxylamine, an important prebiotic molecule, and glycolaldehyde, the smallest sugar, is discussed. These reactions are particularly relevant during the dark ages of star and planet formation, i.e., when the role of UV light is restricted. A quantitative characterization of such processes is only possible through dedicated laboratory studies, i.e., under full control of a large set of parameters such as temperature, atom-flux, and ice morphology. The resulting numbers, physical and chemical constants, e.g., barrier heights, reaction rates and branching ratios, provide information on the molecular processes at work and are needed as input for astrochemical models, in order to bridge the timescales t...

  19. Enzymatic Reactions in Microfluidic Devices

    Ristenpart, W. D.; Wan, J.; Stone, H. A.


    We establish simple scaling laws for enzymatic reactions in microfluidic devices, and we demonstrate that kinetic parameters obtained conventionally using multiple stop-flow experiments may instead be extracted from a single microfluidic experiment. Introduction of an enzyme and substrate species in different arms of a Y-shaped channel allows the two species to diffuse across the parallel streamlines and to begin reacting. Measurements of the product concentration versus distance down the channel provide information about the kinetics of the reaction. In the limit where the enzyme is much larger (and thus less diffusive) than the substrate, we show that near the entrance the total amount of product (P) formed varies as a power law in the distance x down the channel. For reactions that follow standard Michaelis-Menten kinetics, the power law takes the form P˜(Vmax/Km) x^5/2, where Vmax and Km are the maximum reaction rate and Michaelis constant respectively. If a large excess of substrate is used, then Km is identified by measuring Vmax far downstream where the different species are completely mixed by diffusion. Numerical simulations and experiments using the bioluminescent reaction between luciferase and ATP as a model system are both shown to accord with the model. We discuss the implications for significant savings in the amount of time and enzyme required for determination of kinetic parameters.

  20. Toxicologically relevant phthalates in food.

    Kappenstein, Oliver; Vieth, Bärbel; Luch, Andreas; Pfaff, Karla


    Various phthalates have been detected in a wide range of food products such as milk, dietary products, fat-enriched food, meat, fish, sea food, beverages, grains, and vegetables as well as in breast milk. Here we present an overview on toxicologically considerable phthalate levels in food reported in the literature. The most common phthalates detected are di-(2-ethylhexyl) phthalate (DEHP), di-n-butyl phthalate (DnBP), and di-isobutyl phthalate (DiBP). Milk analyses demonstrate that background levels in unprocessed milk are usually low. However, during processing the phthalate contents may significantly increase due to migration from plastic materials in contact with food. Among dietary products fat-enriched food such as cheese and cream were identified with highest levels of DEHP. Plasticized PVC from tubes, conveyor belts, or disposable gloves used in food processing is an important source for contamination of food, especially of fatty food. Paper and cardboard packaging made from recycled fibers are another important source of contamination. In addition, gaskets used in metal lids for glass jars have been identified as possible source for the contamination of foodstuffs with phthalates. The highest concentrations of DEHP reported (>900 mg kg(-1)) were detected in food of high fat content stored in such glass jars. Beyond classical food, DEHP and DnBP were identified in human breast milk samples as the main phthalate contaminants. Phthalate monoesters and some oxidative metabolites were also quantified in breast milk.

  1. "Gastric cytoprotection" is still relevant.

    Szabo, Sandor


    rapid vascular changes (e.g. increased VP and blood flow), followed by cellular events (e.g. infiltration by acute and chronic inflammatory cells). Thus, PG and histamine, by increasing VP create a perivascular edema that dilutes and delays toxic agents reaching the subepithelial capillaries. Otherwise, damaging chemicals may induce severe early vascular injury resulting in blood flow stasis, hypoxia, and necrosis of surrounding epithelial and mesenchymal cells. In this complex response, increased mucus and/or bicarbonate secretion seem to cause luminal dilution of gastrotoxic chemicals that is further reinforced by a perivascular, histodilutional component. This mechanistic explanation would encompass the protective actions of diverse agents as PG, small doses of histamine, motility stimulants, and dilute irritants (i.e. "adaptive cytoprotection"). Thus, although markedly increased VP is pathologic, slight increase in VP seems to be protective, that is, a key element in the complex pathophysiologic response during acute gastroprotection. Over the years, "gastroprotection" was also applied to accelerated healing of chronic gastroduodenal ulcers without reduction of acid secretion. The likely main mechanism here is the binding of angiogenic growth factors (e.g. basic fibroblast growth factor, vascular endothelial growth factor) to the heparin-like structures of sucralfate and sofalcone. Thus, despite intensive research of the last 30 years, gastroprotection is incompletely understood, and we are still far away from effectively treating Helicobacter pylori-negative ulcers and preventing nonsteroidal anti-inflammatory drugs-caused erosions and ulcers in the upper and lower gastrointestinal tract; hence "gastric cytoprotection" research is still relevant.

  2. MEMS Lubrication by In-Situ Tribochemical Reactions From the Vapor Phase.

    Dugger, Michael Thomas; Asay, David B.; Kim, Seong H.


    Vapor Phase Lubrication (VPL) of silicon surfaces with pentanol has been demonstrated. Two potential show stoppers with respect to application of this approach to real MEMS devices have been investigated. Water vapor was found to reduce the effectiveness of VPL with alcohol for a given alcohol concentration, but the basic reaction mechanism observed in water-free environments is still active, and devices operated much longer in mixed alcohol and water vapor environments than with chemisorbed monolayer lubricants alone. Complex MEMS gear trains were successfully lubricated with alcohol vapors, resulting in a factor of 104 improvement in operating life without failure. Complex devices could be made to fail if operated at much higher frequencies than previously used, and there is some evidence that the observed failure is due to accumulation of reaction products at deeply buried interfaces. However, if hypothetical reaction mechanisms involving heated surfaces are valid, then the failures observed at high frequency may not be relevant to operation at normal frequencies. Therefore, this work demonstrates that VPL is a viable approach for complex MEMS devices in conventional packages. Further study of the VPL reaction mechanisms are recommended so that the vapor composition may be optimized for low friction and for different substrate materials with potential application to conventionally fabricated, metal alloy parts in weapons systems. Reaction kinetics should be studied to define effective lubrication regimes as a function of the partial pressure of the vapor phase constituent, interfacial shear rate, substrate composition, and temperature.

  3. Theoretical research relevant to medium energy upgrades and experiments

    Goldman, T.; Benesh, C.; Carlson, J. [and others


    This is the final report of a three-year, Laboratory-Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). This work provides theoretical research results for sources of pions, neutrons, neutrinos and heavy ions. The authors have undertaken specific calculations in neutrino-nucleus scattering and to analyze constraints on exotic decays relevant to the study of neutrino oscillations. They have also performed calculations regarding neutrino cosmology and astrophysics relevant to the experimental study of neutrino masses. They analyzed the constraints of data on T-violation in neutron decay and the nucleon-nucleon (NN) interaction which will be important for the understanding of experiments with cold and ultra-cold neutrons. They completed several specific calculations which were essential to predict (pion, kaon) hypernuclear production and pion-induced reactions studying baryonic resonances. They also calculated the nuclear spectroscopy of nuclei far from stability that can be studied experimentally.

  4. Specificity of reflex adaptation for task-relevant variability.

    Franklin, David W; Wolpert, Daniel M


    The motor system responds to perturbations with reflexes, such as the vestibulo-ocular reflex or stretch reflex, whose gains adapt in response to novel and fixed changes in the environment, such as magnifying spectacles or standing on a tilting platform. Here we demonstrate a reflex response to shifts in the hand's visual location during reaching, which occurs before the onset of voluntary reaction time, and investigate how its magnitude depends on statistical properties of the environment. We examine the change in reflex response to two different distributions of visuomotor discrepancies, both of which have zero mean and equal variance across trials. Critically one distribution is task relevant and the other task irrelevant. The task-relevant discrepancies are maintained to the end of the movement, whereas the task-irrelevant discrepancies are transient such that no discrepancy exists at the end of the movement. The reflex magnitude was assessed using identical probe trials under both distributions. We find opposite directions of adaptation of the reflex response under these two distributions, with increased reflex magnitudes for task-relevant variability and decreased reflex magnitudes for task-irrelevant variability. This demonstrates modulation of reflex magnitudes in the absence of a fixed change in the environment, and shows that reflexes are sensitive to the statistics of tasks with modulation depending on whether the variability is task relevant or task irrelevant.

  5. A clinical analysis of monitoring vancomycin plasma concentration and adverse reactions in 32 cases of elderly patients%32例老年患者万古霉素血药浓度监测与不良反应的临床分析

    付晶; 施阳; 荆晓明; 王一凡; 王雷


    with adverse reactions in treatment of elderly patients. Methods The clinical records of 32 patients aged over 70 years admitted in the Emergency Medical Department of Sichuan Provincial People's Hospital were collected. Based on the diagnosis and laboratory examinations on admission, the patients were treated with cefoperazone+sulbactam or moxifloxacin, while in patients with severe infections, intravenous drip of carbapenem antibacterial drugs were given. After treatment for 3-5 days, when no effective results were obtained, according to the pathogenic results achieved from cultures of blood, sputum, secretions, catheter, etc, the corresponding treatment was given. If the infection was caused by positive bacteria mainly methicillin-resistant Staphylococcus aureus (MRSA) sensitive to vancomycin, the original antibiotic was replaced by vancomycin or vancomycin combined with other antibiotic; intravenous drip of vancomycin 1 g in 250 mL normal saline was given, once in 12 hours, with a speed of 10 mg/min or not over 15 mg/min. The function of liver and kidney, and auditory impairment were observed, and the correlation between vancomycin plasma concentration and adverse reactions was analyzed. Results The total incidence of adverse reactions in elderly patients with different serum vancomycin trough concentrations was 37.50%(12/32) in which the highest incidence was kidney damage 18.75%(6/32) followed by the hearing loss 9.38%(3/32) and liver damage 9.38%(3/32). There were no statistical significant differences in the rates of adverse reactions among the different vancomycin trough concentrations (20 mg/L) and [37.50%(6/16), 38.46%(5/13), 33.33%(1/3), all P>0.05], that meant along with the increase of vancomycin concentration, no tendency of increment of adverse reactions was seen. Of the 32 cases, there were 13 treated by vancomycin combined with other antibiotic, the combination rate being 40.63%. There were 2 cases of hepatic impairment (11.83%), 1 case of renal

  6. Classical Radiation Reaction in Particle-In-Cell Simulations

    Vranic, Marija; Fonseca, Ricardo A; Silva, Luis O


    Under the presence of ultra high intensity lasers or other intense electromagnetic fields the motion of particles in the ultrarelativistic regime can be severely affected by radiation reaction. The standard particle-in-cell (PIC) algorithms do not include radiation reaction effects. Even though this is a well known mechanism, there is not yet a definite algorithm nor a standard technique to include radiation reaction in PIC codes. We have compared several models for the calculation of the radiation reaction force, with the goal of implementing an algorithm for classical radiation reaction in the Osiris framework, a state-of-the-art PIC code. The results of the different models are compared with standard analytical results, and the relevance/advantages of each model are discussed. Numerical issues relevant to PIC codes such as resolution requirements, application of radiation reaction to macro particles and computational cost are also addressed. The Landau and Lifshitz reduced model is chosen for implementatio...

  7. Astrophysically Relevant Neutron Capture near the Border of Stability

    Mohr, P J; Beer, H


    The neutron capture cross section on $^{26}$Mg was measured in the astrophysically relevant energy region from 25 keV to 220 keV. The experimental results agree well with a calculation using the Direct Capture (DC) model together with systematic folding potentials. This experiment confirms for the $^{26}$Mg(n,$\\gamma$)$^{27}$Mg reaction that the DC process is at least comparable to the Compound--Nucleus (CN) process. The reliability of DC calculations is discussed, and we present some ideas for future experiments which could reduce the theoretical uncertainties of DC calculations.

  8. Accelerated redox reaction between chromate and phenolic pollutants during freezing

    Ju, Jinjung; Kim, Jaesung [Department of Environmental Sciences and Biotechnology, Hallym University, Chuncheon, Gangwon-do 24252 (Korea, Republic of); Vetráková, Ľubica [Department of Chemistry and Research Centre for Toxic Compounds in the Environment (RECETOX), Faculty of Science, Masaryk University, Kamenice 5, 625 00 Brno (Czech Republic); Seo, Jiwon [School of Urban and Environmental Engineering, Ulsan National Institute of Science and Technology (UNIST), Ulsan 44919 (Korea, Republic of); Heger, Dominik [Department of Chemistry and Research Centre for Toxic Compounds in the Environment (RECETOX), Faculty of Science, Masaryk University, Kamenice 5, 625 00 Brno (Czech Republic); Lee, Changha [School of Urban and Environmental Engineering, Ulsan National Institute of Science and Technology (UNIST), Ulsan 44919 (Korea, Republic of); Yoon, Ho-Il [Korea Polar Research Institute (KOPRI), Incheon 21990 (Korea, Republic of); Kim, Kitae, E-mail: [Korea Polar Research Institute (KOPRI), Incheon 21990 (Korea, Republic of); Kim, Jungwon, E-mail: [Department of Environmental Sciences and Biotechnology, Hallym University, Chuncheon, Gangwon-do 24252 (Korea, Republic of)


    Highlights: • Redox conversion of 4-CP/Cr(VI) was significantly accelerated during freezing. • Accelerated redox conversion in ice is ascribed to the freeze concentration effect. • 4-CP, Cr(VI), and protons are concentrated in the liquid brine by freezing. • Redox conversions of various phenolic pollutants/Cr(VI) were significant in ice. • Freezing-accelerated redox conversion was observed in real polluted water. - Abstract: The redox reaction between 4-chlorophenol (4-CP) and chromate (Cr(VI)) (i.e., the simultaneous oxidation of 4-CP by Cr(VI) and reduction of Cr(VI) by 4-CP) in ice (i.e., at −20 °C) was compared with the corresponding reaction in water (i.e., at 25 °C). The redox conversion of 4-CP/Cr(VI), which was negligible in water, was significantly accelerated in ice. This accelerated redox conversion of 4-CP/Cr(VI) in ice is ascribed to the freeze concentration effect occurring during freezing, which excludes solutes (i.e., 4-CP and Cr(VI)) and protons from the ice crystals and subsequently concentrates them in the liquid brine. The concentrations of Cr(VI) and protons in the liquid brine were confirmed by measuring the optical image and the UV–vis absorption spectra of cresol red (CR) as a pH indicator of frozen solution. The redox conversion of 4-CP/Cr(VI) was observed in water when the concentrations of 4-CP/protons or Cr(VI)/protons increased by 100/1000-fold. These results corroborate the freeze concentration effect as the reason for the accelerated redox conversion of 4-CP/Cr(VI) in ice. The redox conversion of various phenolic pollutants/Cr(VI) and 4-CP/Cr(VI) in real wastewater was successfully achieved in ice, which verifies the environmental relevance and importance of freezing-accelerated redox conversion of phenolic pollutants/Cr(VI) in cold regions.

  9. Heuristics-Guided Exploration of Reaction Mechanisms.

    Bergeler, Maike; Simm, Gregor N; Proppe, Jonny; Reiher, Markus


    For the investigation of chemical reaction networks, the efficient and accurate determination of all relevant intermediates and elementary reactions is mandatory. The complexity of such a network may grow rapidly, in particular if reactive species are involved that might cause a myriad of side reactions. Without automation, a complete investigation of complex reaction mechanisms is tedious and possibly unfeasible. Therefore, only the expected dominant reaction paths of a chemical reaction network (e.g., a catalytic cycle or an enzymatic cascade) are usually explored in practice. Here, we present a computational protocol that constructs such networks in a parallelized and automated manner. Molecular structures of reactive complexes are generated based on heuristic rules derived from conceptual electronic-structure theory and subsequently optimized by quantum-chemical methods to produce stable intermediates of an emerging reaction network. Pairs of intermediates in this network that might be related by an elementary reaction according to some structural similarity measure are then automatically detected and subjected to an automated search for the connecting transition state. The results are visualized as an automatically generated network graph, from which a comprehensive picture of the mechanism of a complex chemical process can be obtained that greatly facilitates the analysis of the whole network. We apply our protocol to the Schrock dinitrogen-fixation catalyst to study alternative pathways of catalytic ammonia production.

  10. Impact of reaction conditions on grafting acrylamide onto starch

    We have explored the radical initiated graft polymerization reaction of acrylamide onto starch where the solvent, concentration, temperature and reaction times were varied. We have found that the morphology of the resulting grafted polymer is dramatically different and is dependent on the reaction c...

  11. Double Pion Production Reactions

    Oset, E; Cano, F; Hernández, E; Kamalov, S S; Nacher, J C; Tejedor, J A G


    We report on reactions producing two pions induced by real and virtual photons or nucleons. The role of different resonances in these reactions is emphasized. Novel results on coherent two pion photoproduction in nuclei are also reported.

  12. Microscale Thermite Reactions.

    Arnaiz, Francisco J.; Aguado, Rafael; Arnaiz, Susana


    Describes the adaptation of thermite (aluminum with metal oxides) reactions from whole-class demonstrations to student-run micro-reactions. Lists detailed directions and possible variations of the experiment. (WRM)

  13. Application of Relevance theory to translation



    Within the framework of relevance theory, translation is regarded as a relevance-seeking communication. It involves three participant relationships:the source speaker, the translator and the target hearers. The translator is supposed to create a context that the target hearer can infer the intention of the source speaker. Comparing translation theories which fail to pay attention to the relevance between the source speakers and the target hearers, Relevance Theory is a relatively overall account of translation. For one thing, some points concerning the Relevance Theory are capable of facilitating the researches to the present translation field. For another, the information of the original text will be understood and comprehended accurately and promptly on the basis of the relevant theory.

  14. Chemical transport reactions

    Schäfer, Harald


    Chemical Transport Reactions focuses on the processes and reactions involved in the transport of solid or liquid substances to form vapor phase reaction products. The publication first offers information on experimental and theoretical principles and the transport of solid substances and its special applications. Discussions focus on calculation of the transport effect of heterogeneous equilibria for a gas motion between equilibrium spaces; transport effect and the thermodynamic quantities of the transport reaction; separation and purification of substances by means of material transport; and

  15. Towards Quantum Transport for Central Nuclear Reactions

    Danielewicz, Pawel; Barker, Brent


    Nonequilibrium Green's functions represent a promising tool for describing central nuclear reactions. Even at the single-particle level, though, the Green's functions contain more information that computers may handle in the foreseeable future. In this study, we explore slab collisions in one dimension, first in the mean field approximation and demonstrate that only function elements close to the diagonal in arguments are relevant, in practice, for the reaction calculations. This bodes well for the application of the Green's functions to the reactions. Moreover we demonstrate that an initial state for a reaction calculation may be generated through adiabatic transformation of interactions. Finally, we report on our progress in incorporating correlations into the dynamic calculations.

  16. Implications of Relevance Theory to English Reading



    Reading is a style of communication between reader and writer while relevance theory is a new approach to communi⁃cation. Based on relevance theory, we can paraphrase reading as followings: reading comprehension is a process of communica⁃tion between reader and writer; a process of making inference from the ostensive-inference communication; a process of seeking optimal relevance on the part of the reader.

  17. GA(2)LEN skin test study II: clinical relevance of inhalant allergen sensitizations in Europe

    Burbach, G J; Heinzerling, L M; Edenharter, G


    BACKGROUND: Skin prick testing is the standard for diagnosing IgE-mediated allergies. A positive skin prick reaction, however, does not always correlate with clinical symptoms. A large database from a Global Asthma and Allergy European Network (GA(2)LEN) study with data on clinical relevance...... was used to determine the clinical relevance of sensitizations against the 18 most frequent inhalant allergens in Europe. The study population consisted of patients referred to one of the 17 allergy centres in 14 European countries (n = 3034, median age = 33 years). The aim of the study was to assess...... the clinical relevance of positive skin prick test reactions against inhalant allergens considering the predominating type of symptoms in a pan-European population of patients presenting with suspected allergic disease. METHODS: Clinical relevance of skin prick tests was recorded with regard to patient history...

  18. Autocatalysis-driven clock reaction II: kinetics of the pentathionate-periodate reaction.

    Xu, Li; Horváth, Attila K


    The pentathionate-periodate reaction has been investigated by spectrophotometrically monitoring the total amount of iodine evolved in the presence of phosphoric acid/dihydrogen phosphate buffer at 468 nm. The majority of the main characteristics of the title system is very reminiscent of that found recently in the pentathionate-iodate reaction, a system that led us to classify generally the clock reactions. Along with the pentathionate-iodate reaction the title system is proposed to belong to the autocatalysis-driven clock reactions as well. The kinetic model of the pentathionate-iodate system published recently was implemented by the necessary reactions of periodate to compose a 24-step kinetic model in which the mechanisms of the pentathionate-iodine, pentathionate-iodate, bisulfite-periodate, bisulfite-iodate, iodide-periodate, and the well-known Dushman reactions are combined. A thorough analysis revealed that the direct pentathionate-periodate reaction plays a role only to produce iodide ion via a finite sequence of reactions, and once its concentration reaches a certain level, the reaction is almost exclusively governed by the pentathionate-iodine, the iodide-periodate, and the Dushman reactions. As expected strong catalytic effect of the buffer composition is also found that can readily be explained by its well-known catalytic influence on the Dushman reaction.

  19. Reaction systems with precipitation

    Marek Rogalski


    Full Text Available This article proposes expanding Reaction Systems of Ehrenfeucht and Rozenberg by incorporating precipitation reactions into it. This improves the computing power of Reaction Systems by allowing us to implement a stack. This addition enables us to implement a Deterministic Pushdown Automaton.

  20. Relevance: An Interdisciplinary and Information Science Perspective

    Howard Greisdorf


    Full Text Available Although relevance has represented a key concept in the field of information science for evaluating information retrieval effectiveness, the broader context established by interdisciplinary frameworks could provide greater depth and breadth to on-going research in the field. This work provides an overview of the nature of relevance in the field of information science with a cursory view of how cross-disciplinary approaches to relevance could represent avenues for further investigation into the evaluative characteristics of relevance as a means for enhanced understanding of human information behavior.

  1. Biorefining of waste paper biomass: increasing the concentration of glucose by optimising enzymatic hydrolysis.

    Elliston, Adam; Collins, Samuel R A; Faulds, Craig B; Roberts, Ian N; Waldron, Keith W


    Waste copier paper is a potential substrate for the production of glucose relevant for manufacture of platform chemicals and intermediates, being composed of 51 % glucan. The yield and concentration of glucose arising from the enzymatic saccharification of solid ink-free copier paper as cellulosic substrate was studied using a range of commercial cellulase preparations. The results show that in all cellulase preparations examined, maximum hydrolysis was only achieved with the addition of beta-glucosidase, despite its presence in the enzyme mixtures. With the use of Accellerase® (cellulase), high substrate loading decreased conversion yield. However, this was overcome if the enzyme was added between 12.5 and 20 FPU g substrate(-1). Furthermore, this reaction condition facilitated continual stirring and enabled sequential additions (up to 50 % w/v) of paper to be made to the hydrolysis reaction, degrading nearly all (99 %) of the cellulose fibres and increasing the final concentration of glucose whilst simultaneously making high substrate concentrations achievable. Under optimal conditions (50 °C, pH 5.0, 72 h), digestions facilitate the production of glucose to much improved concentrations of up to 1.33 mol l(-1).

  2. Evaluation of the contamination of the river Elbe with organic micropollutants relevant to the aquatic ecosystem. Vol. 2: pesticides with low effect concentrations with regard to the aquatic ecosystem; Erfassung und Beurteilung der Belastung der Elbe mit oekosystemrelevanten Organika. Bd. 2: Pestizide mit niedrigen Effektkonzentrationen im aquatischen Bereich - Entwicklung eines Ion Trap GC/MS{sup 2} Verfahrens

    Gandrass, J.; Zoll, M.; Caba, A.


    In the first part of the research project the status of pollution of chlorinated hydrocarbons (CHC) and pesticides in the Elbe catchment area was evaluated with regard to quality objectives and criteria. For CHC for the first time an extensive overview over the contamination of sediments in the Czech and German part of the Elbe including its main tributairies was achieved. For individual compounds regional hot spots were observed. Major inputs to the Elbe river were derived from differences in characteristic compound pattern. Between 1992 and 1995 a downstream transport of contaminated sediments was supposed due to changed concentrations of individual compounds. However no general decrease of contamination was observed. Existing quality objectives were severely exceeded. A broad screening for 76 pesticides was conducted by analysing time series as well as length profiles. Generally the pesticides showed a high temporal and spatial variability. 42 of the 76 compounds were detected above the limits of determination. From these 28 exceeded at least occasinally the drinking water limit. For a number of compounds quality objectives or criteria with regard to aquatic wildlife were exceeded. For the majority of pesticides either quality objectives were not available or the analytical limits of determination were not sufficiently low to allow a defined assessment. As a consequence in the second part of the research project on Ion Trap GC/MS{sup 2} method was developed, which met the required specifity and sensitivity. Due to matrix-induced enhanced responses for a large number of pesticides, high measurement uncertainties were noticed in the ng/L range. For this reason the Ion Trap GC/MS{sup 2} method could not finally be validated. (orig.) [German] Im ersten Teil des Forschungsvorhabens erfolgte eine Bestandsaufnahme und Bewertung hinsichtlich der Belastung mit schwerfluechtigen Chlorkohlenwasserstoffen (SCKW) und Pestiziden im Elbeeinzugsgebiet. Fuer die Stoffgruppe der

  3. Safe design of cooled tubular reactors for exothermic, multiple reactions. Consecutive reactions

    Westerterp, K.R.; Overtoom, R.R.M.


    The model of the pseudo-homogeneous, one-dimensional, cooled tubular reactor is applied to two consecutive, irreversible first order reactions. A criterion is derived to obtain a desired integral yield. Based on this criterion three requirements are formulated, which enable us to choose the relevant

  4. Attention bias for paranoia-relevant visual stimuli in schizophrenia.

    Moritz, Steffen; Laudan, Anna


    A number of studies indicate that patients with schizophrenia share a bias for paranoia-relevant material. The presence of an attentional bias for such stimuli would be of utter importance for our pathogenetic understanding of the disorder in view of ample evidence that patients with schizophrenia gather little information before arriving at strong conclusions: A both scarce and affectively biased data selection of available information may heavily distort its inner representation and thus prompt the formation of false beliefs. To date, the profile of this putative attentional bias in schizophrenia (e.g., automatic vs. controlled; hypervigilance towards vs. problems to disengage from such stimuli) is not fully uncovered. To shed light on this aspect of information processing in schizophrenia, we administered a novel task based on the inhibition of return paradigm (IOR). Twenty-four schizophrenia patients and thirty-four healthy controls were presented neutral (e.g., cup), anxiety-relevant (e.g., shark), and paranoia-relevant cue pictures (e.g., gun) at either of two possible locations. Subsequent to either a short or long interval, a target appeared at the same or opposite location. Participants were requested to press a spatially corresponding button. Both currently paranoid and nonparanoid schizophrenia patients responded faster to all kinds of targets following paranoia-relevant pictures, that is, such stimuli speeded reaction times irrespective of the cue-target interval and spatial correspondence. This indicates that paranoia-relevant information generally alerts patients more than other stimuli and facilitates processing of subsequent information. Possible implications of this finding for our understanding of delusion formation and maintenance are outlined.

  5. Clinical relevance of [i]Corylus[/i] pollen in Poznań, western Poland

    Łukasz Grewling


    Full Text Available Background. In Central Europe, hazel ([i]Corylus[/i] sp. pollen is considered to be an important aeroallergen in early spring. Objective. This study examines hazel pollen levels in Poznań, western Poland, and the clinical relevance of this aeroallergen in the city. Methods. [i]Corylus[/i] pollen data (1996–2010 were obtained by volumetric spore trap located near the centre of Poznań. Clinical data (2006–2010, i.e. skin prick test (SPT and allergen-specific IgE measurements (asIgE, were supplied by the Allergy Diseases Diagnostic Centre in Poznań. Results. Mean diurnal hazel pollen concentrations peaked around 14:00–16:00 when mean bi-hourly pollen concentrations were ~60 P m-3. Onset of the hazel pollen season varied up to 87 days annually, and was significantly (r=–0.647; p<0.01 related to mean maximum temperature during late December. SPT data revealed that ~11% of allergy patients had positive skin reactions to [i]Corylus[/i] pollen allergens, and most of these (94.4% reacted to pollen allergens from other members of the Betulaceae family – alder or birch. Of those sensitized, 53% suffered from atopic dermatitis. Of patients examined for serum asIgE, 26.0% had asIgE measurements in classes 5 and 6. Conclusions. Hazel pollen has a detrimental effect on the allergic population of Poznań, with more than half of those sensitised to hazel pollen allergens showing symptoms of atopic dermatitis. Hazel pollen concentrations reach levels recognized as being able to induce allergy symptoms, especially in the afternoon and early evening when many people are returning home from work. The cross-reactivity with other members of the Fagales order also increases the allergenic potential of hazel pollen.

  6. Studies on the Simultaneous Formation of Aroma-Active and Toxicologically Relevant Vinyl Aromatics from Free Phenolic Acids during Wheat Beer Brewing.

    Langos, Daniel; Granvogl, Michael


    During the brewing process of wheat beer, the desired aroma-active vinyl aromatics 2-methoxy-4-vinylphenol and 4-vinylphenol as well as the undesired and toxicologically relevant styrene are formed from their respective precursors, free ferulic acid, p-coumaric acid, and cinnamic acid, deriving from the malts. Analysis of eight commercial wheat beers revealed high concentrations of 2-methoxy-4-vinylphenol and 4-vinylphenol always in parallel with high concentrations of styrene or low concentrations of the odorants in parallel with low styrene concentrations, suggesting a similar pathway. To better understand the formation of these vinyl aromatics, each process step of wheat beer brewing and the use of different strains of Saccharomyces cerevisiae were evaluated. During wort boiling, only a moderate decarboxylation of free phenolic acids and formation of desired and undesired vinyl aromatics were monitored due to the thermal treatment. In contrast, this reaction mainly occurred enzymatically catalyzed during fermentation with S. cerevisiae strain W68 with normal Pof(+) activity (phenolic off-flavor) resulting in a wheat beer eliciting the typical aroma requested by consumers due to high concentrations of 2-methoxy-4-vinylphenol (1790 μg/L) and 4-vinylphenol (937 μg/L). Unfortunately, also a high concentration of undesired styrene (28.3 μg/L) was observed. Using a special S. cerevisiae strain without Pof(+) activity resulted in a significant styrene reduction (beer aroma.

  7. Ranking Music Data by Relevance and Importance

    Ruxanda, Maria Magdalena; Nanopoulos, Alexandros; Jensen, Christian Søndergaard


    the music based on its relevance and importance. The fusion is controlled by a single parameter, which can be intuitively tuned by the user. The notion of authoritative music among relevant music is introduced, and social media mined from the Web is used in an innovative manner to determine both...

  8. Modelling Complex Relevance Spaces with Copulas

    C. Eickhoff (Carsten); A.P. de Vries (Arjen)


    htmlabstractModern relevance models consider a wide range of criteria in order to identify those documents that are expected to satisfy the user's information need. With growing dimensionality of the underlying relevance spaces the need for sophisticated score combination and estimation schemes

  9. Alligning vertical collection relevance with user intent

    Zhou, Ke; Demeester, Thomas; Nguyen, Dong; Hiemstra, Djoerd; Trieschnigg, Dolf


    Selecting and aggregating different types of content from multiple vertical search engines is becoming popular in web search. The user vertical intent, the verticals the user expects to be relevant for a particular information need, might not correspond to the vertical collection relevance, the vert

  10. Relevance and problem choice in design science

    Wieringa, Roelf J.


    The supposed opposition of rigor versus relevance is based on the mistaken idea that rigor consists of linear technology transfer combined with positivistic science, and ignores the context-dependence of relevance as well as the incorporation of conditions of practice necessary for applicability of

  11. CMIC@TREC-2009: Relevance Feedback Track


    Carbonell and Goldstein [2] suggested the so-called Maximal Marginal Relevance (MMR) which attempts to reduce redundancy while maintaining relevance...Search and Data Mining, (Barcelona, Spain: ACM, 2009), pp. 5-14. 2. Carbonell , J. and Goldstein, J. The use of MMR, diversity-based reranking for

  12. Alligning Vertical Collection Relevance with User Intent

    Zhou, Ke; Demeester, Thomas; Nguyen, Dong-Phuong; Hiemstra, Djoerd; Trieschnigg, Rudolf Berend

    Selecting and aggregating different types of content from multiple vertical search engines is becoming popular in web search. The user vertical intent, the verticals the user expects to be relevant for a particular information need, might not correspond to the vertical collection relevance, the

  13. 49 CFR 1150.13 - Relevant dates.


    ... 49 Transportation 8 2010-10-01 2010-10-01 false Relevant dates. 1150.13 Section 1150.13 Transportation Other Regulations Relating to Transportation (Continued) SURFACE TRANSPORTATION BOARD, DEPARTMENT... Designated Operators § 1150.13 Relevant dates. The exact dates of the period of operation which have...

  14. Visualizing biological reaction intermediates with DNA curtains

    Zhao, Yiling; Jiang, Yanzhou; Qi, Zhi


    Single-molecule approaches have tremendous potential analyzing dynamic biological reaction with heterogeneity that cannot be effectively accessed via traditional ensemble-level biochemical approaches. The approach of deoxyribonucleic acid (DNA) curtains developed by Dr Eric Greene and his research team at Columbia University is a high-throughput single-molecule technique that utilizes fluorescent imaging to visualize protein–DNA interactions directly and allows the acquisition of statistically relevant information from hundreds or even thousands of individual reactions. This review aims to summarize the past, present, and future of DNA curtains, with an emphasis on its applications to solve important biological questions.

  15. 甲氨蝶呤治疗侵蚀性葡萄胎的血药浓度监测及不良反应观察%Monitoring drug concentration and adverse reactions of methotrexate in the treatment of invasive hydatidiform mole

    宁俊红; 吴志刚; 雷莹; 张若梅


    Objective:To investigate the necessity of monitoring methotrexate (MTX) concentration and its adverse reactions in the treatment of invasive hydatidiform mole. Methods:Ten patients diagnosed as invasive hydatidiform mole were given intramuscular methotrexate 0.4 mg·kg-1·d-1 at the same time every day for five days. Blood concentrations of methotrexate were determined at 24, 72, 120 hours after the first intramuscular injection and ADRs induced by MTX were observed. Results:After one or more cycles of treatment, nine patients were cured, one patient changed the chemotherapy due to poor efficacy. Methotrexate concentrations in thirty plasma from ten patients were lower than the safety value. ADRs occurred in six patients including one patient with severe bone marrow suppression. Conclusion:It's not necessary to monitor methotrexate blood concentration in the treatment of invasive hydatidiform mole and use calcium folinate for ADRs. Although the plasma concentration was very low, ADRs induced by methotrexate should be paid more attention to.%  目的:探讨甲氨蝶呤治疗侵蚀性葡萄胎时,监测其血药浓度的必要性及不良反应的发生情况.方法:10例确诊为侵蚀性葡萄胎的患者,肌注甲氨蝶呤0.4 mg·kg-1·d-1,每天同一时间肌注,连续肌注5 d,并于第一次肌注后的24,72,120 h取2 mL静脉血,测定甲氨蝶呤的血药浓度,同时观察不良反应.结果:经过一个或多个周期的治疗后,9名患者治愈,1名患者由于疗效不佳,改用其他化疗方案.10例患者共30份甲氨蝶呤的血药浓度值均低于安全值;10例患者中,6例出现不良反应,其中1例患者出现严重的骨髓抑制.结论:治疗侵蚀性葡萄胎时,监测甲氨蝶呤血药浓度的意义不大,没有必要用四氢叶酸钙解毒;甲氨蝶呤的血药浓度很低时,仍然需要关注其所致的不良反应.

  16. Relevance ranking for vertical search engines

    Chang, Yi


    In plain, uncomplicated language, and using detailed examples to explain the key concepts, models, and algorithms in vertical search ranking, Relevance Ranking for Vertical Search Engines teaches readers how to manipulate ranking algorithms to achieve better results in real-world applications. This reference book for professionals covers concepts and theories from the fundamental to the advanced, such as relevance, query intention, location-based relevance ranking, and cross-property ranking. It covers the most recent developments in vertical search ranking applications, such as freshness-based relevance theory for new search applications, location-based relevance theory for local search applications, and cross-property ranking theory for applications involving multiple verticals. It introduces ranking algorithms and teaches readers how to manipulate ranking algorithms for the best results. It covers concepts and theories from the fundamental to the advanced. It discusses the state of the art: development of ...

  17. Hypersensitivity reactions and contrast medium injection: Are they always related?

    Boehm, Ingrid, E-mail: [Department of Radiology, Philipps University of Marburg, Baldingerstrasse, 35039 Marburg (Germany); Alfke, Heiko [Department of Radiology, Klinikum Luedenscheid, Luedenscheid (Germany); Klose, Klaus Jochen [Department of Radiology, Philipps University of Marburg, Baldingerstrasse, 35039 Marburg (Germany)


    Background: Hypersensitivity (allergic or non-allergic) reactions that occur after contrast medium (CM) injection are usually related to the CM. Recent studies, and case reports lack the analysis of alternate causes that could be also responsible in individual cases. Patients and methods: We investigated the individual relevant factor/causative agent of adult patients with hypersensitivity reactions that occurred in radiological units during CM-enhanced procedures (CT, angiography, urography, or MR-examinations). Both immediate and non-immediate (delayed) reactions were included. To find out the relevant agent a detailed patients' history was carefully analyzed. In addition, the records were retrospectively reviewed, and if indicated and possible laboratory (e.g. basophil activation test) and skin tests (e.g. prick) and/or provocations with CM-injections under routine conditions were performed. Results: 38 patients (men n = 21) suspected for CM-hypersensitivity reactions were identified. These reactions were in most cases mild (n = 21), moderate reactions occurred in 13 cases, and four patients had severe reactions. In 28 patients the reactions were induced by the CM (iodinated CM in 25 cases). Four patients had reactions that were not CM-related (latex allergy, adenosine reaction, vasovagal reaction, unknown cause) and in six cases the reaction was partly CM-related (immunological activation was present due to the patients' diseases). Conclusion: Our data support the hypothesis that in CM-enhanced procedures not only contrast materials but also a broad range of other factors may also induce hypersensitivity reactions. Therefore, the number of CM-induced hypersensitivity is smaller than initially suspected. The knowledge of the cause of a reaction is essential to effectively prevent its recurrence and to improve safety aspects in patients undergoing CM-injection. Larger trials should be performed to more specifically assess alternate causes in patients

  18. A possible candidate to be classified as an autocatalysis-driven clock reaction: kinetics of the pentathionate-iodate reaction.

    Xu, Li; Horváth, Attila K


    The pentathionate-iodate reaction has been investigated by spectrophotometrically monitoring the formation of the total amount of iodine at 468 nm in the presence of phosphoric acid/dihydrogen phosphate buffer. We noticed that iodine forms only after a fairly long time lag, and the inverse of time necessary to produce a certain amount of iodine is linearly proportional to the initial concentration of iodate ion and the square of the hydrogen ion concentration, while depending complexly on the concentration of substrate pentathionate. This reaction can therefore be treated as a clock reaction but differs from the original Landolt reaction in the sense that substrate pentathionate and the clock species iodine coexist for a relatively long time--due to their relatively slow direct reaction--depending on the experimental circumstances. Furthermore, we also provided experimental evidence that iodide ion acts as an autocatalyst of the system. A 14-step kinetic model is proposed in which the mechanisms of the pentathionate-iodine, bisulfite-iodate, and the well-known Dushman reactions are combined. A thorough analysis revealed that the direct pentathionate-iodate reaction plays a role only to produce iodide ions via a finite sequence of reactions, and once its concentration reaches a certain level, the reaction is almost exclusively governed by the pentathionate-iodine and the Dushman reactions. As expected, a strong catalytic effect of the buffer composition is also found that can readily be explained by its well-known catalytic influence on the original Dushman reaction.

  19. Looking for chemical reaction networks exhibiting a drift along a manifold of marginally stable states.

    Brogioli, Doriano


    I recently reported some examples of mass-action equations that have a continuous manifold of marginally stable stationary states [Brogioli, D., 2010. Marginally stable chemical systems as precursors of life. Phys. Rev. Lett. 105, 058102; Brogioli, D., 2011. Marginal stability in chemical systems and its relevance in the origin of life. Phys. Rev. E 84, 031931]. The corresponding chemical reaction networks show nonclassical effects, i.e. a violation of the mass-action equations, under the effect of the concentration fluctuations: the chemical system drifts along the marginally stable states. I proposed that this effect is potentially involved in abiogenesis. In the present paper, I analyze the mathematical properties of mass-action equations of marginally stable chemical reaction networks. The marginal stability implies that the mass-action equations obey some conservation law; I show that the mathematical properties of the conserved quantity characterize the motion along the marginally stable stationary state manifold, i.e. they allow to predict if the fluctuations give rise to a random walk or a drift under the effect of concentration fluctuations. Moreover, I show that the presence of the drift along the manifold of marginally stable stationary-states is a critical property, i.e. at least one of the reaction constants must be fine tuned in order to obtain the drift.

  20. Quantification of the temperature sensitivity of three substrate-enzyme pairings of soil-ecological relevance

    Lehmeier, C.; Ballantyne, F.; Billings, S. A.


    Soil microbes obtain resources from substrates exhibiting variation in structural complexity, carbon to nitrogen ratio (C:N), and energy requirements for decomposition. Theory of enzyme kinetics predicts that the activation energy required for substrate decomposition decreases with increasing temperature, and that the magnitude of the decrease increases with structural complexity of the substrate. However, the temperature sensitivity of important substrate-enzyme reactions at soil-relevant temperatures is largely unknown. Predicting soil organic matter (SOM) decay with rising temperature may be further complicated by changing microbial resource uptake due to 1) direct physiological responses to temperature shifts and 2) altered C and N availability imposed by changing patterns of enzymatic SOM decomposition. This could generate departures from expectations of the overall temperature response of SOM decay. Thus, quantification of both factors (changes in single reaction rates and in microbial community functioning) is important to understand the mechanisms governing soil-atmosphere CO2 fluxes with rising temperature. Here, we quantify the temperature sensitivity of substrate-enzyme pairings relevant to global soil biogeochemistry: (1) β-D-cellobioside (BC) and β-Glucosidase (BGase); (2) N-acetyl-β-D-glucosaminide (NAG) and β-N-Acetyl glucosaminidase (NAGase) and (3) 3,4-Dihydroxy-L-phenylalanine (L-Dopa) and peroxidase (representative of breakdown products of cellulose, chitin and lignin and associated enzymes, respectively). We assessed reaction rates of BC/BGase and NAG/NAGase with fluorophotometric techniques. Both pairings exhibited Michaelis-Menten-like kinetics. When neither enzyme nor substrate was limiting, maximum specific activity (Vmax) of BGase was 28 μmol h-1 unit -1 at 27 °C, approximately three orders of magnitude higher than NAGase (2.5 nmol h-1 unit-1 at 25 °C). Spectrophomometric measurements of L-Dopa degradation rates did not yield

  1. Neutrino-nucleus reactions in supernovae

    Dzhioev, Alan A.; Vdovin, A. I.


    We study thermal effects on neutrino-nucleus reactions occurring under supernova conditions. The approach we use is based on the QRPA extended to finite temperature by the thermofield dynamics formalism. For the relevant supernova conditions we calculate inelastic neutrino scattering and neutrino absorption cross sections for two sample nuclei, 56Fe and 82Ge. In addition, we apply the approach to examine the rate of neutrino-antineutrino pair emission by hot nuclei.

  2. Neutrino-nucleus reactions in supernovae

    Dzhioev Alan A.


    Full Text Available We study thermal effects on neutrino-nucleus reactions occurring under supernova conditions. The approach we use is based on the QRPA extended to finite temperature by the thermofield dynamics formalism. For the relevant supernova conditions we calculate inelastic neutrino scattering and neutrino absorption cross sections for two sample nuclei, 56Fe and 82Ge. In addition, we apply the approach to examine the rate of neutrino-antineutrino pair emission by hot nuclei.

  3. Noncanonical Reactions of Flavoenzymes

    Pablo Sobrado


    Full Text Available Enzymes containing flavin cofactors are predominantly involved in redox reactions in numerous cellular processes where the protein environment modulates the chemical reactivity of the flavin to either transfer one or two electrons. Some flavoenzymes catalyze reactions with no net redox change. In these reactions, the protein environment modulates the reactivity of the flavin to perform novel chemistries. Recent mechanistic and structural data supporting novel flavin functionalities in reactions catalyzed by chorismate synthase, type II isopentenyl diphosphate isomerase, UDP-galactopyranose mutase, and alkyl-dihydroxyacetonephosphate synthase are presented in this review. In these enzymes, the flavin plays either a direct role in acid/base reactions or as a nucleophile or electrophile. In addition, the flavin cofactor is proposed to function as a “molecular scaffold” in the formation of UDP-galactofuranose and alkyl-dihydroxyacetonephosphate by forming a covalent adduct with reaction intermediates.

  4. Reaction cross-section predictions for nucleon induced reactions

    Nobre, G P A; Escher, J E; Dietrich, F S


    A microscopic calculation of the optical potential for nucleon-nucleus scattering has been performed by explicitly coupling the elastic channel to all the particle-hole (p-h) excitation states in the target and to all relevant pickup channels. These p-h states may be regarded as doorway states through which the flux flows to more complicated configurations, and to long-lived compound nucleus resonances. We calculated the reaction cross sections for the nucleon induced reactions on the targets $^{40,48}$Ca, $^{58}$Ni, $^{90}$Zr and $^{144}$Sm using the QRPA description of target excitations, coupling to all inelastic open channels, and coupling to all transfer channels corresponding to the formation of a deuteron. The results of such calculations were compared to predictions of a well-established optical potential and with experimental data, reaching very good agreement. The inclusion of couplings to pickup channels were an important contribution to the absorption. For the first time, calculations of excitatio...

  5. Measuring astrophysically relevant 36Cl production cross sections

    Anderson, Tyler; Skulski, Michael; Ostdiek, Karen; Lu, Wenting; Clark, Adam; Nelson, Austin; Beard, Mary; Collon, Philippe


    The short-lived radionuclide 36Cl (t1 / 2 = 0 . 301 Ma) is known to have existed in the Early Solar System (ESS), and evaluating its production sources can lead to better understanding of the processes taking place in ESS formation and their timescales. The X-wind model is used to explain 36Cl production via solar energetic particles from the young Sun, but is lacking empirical data for many relevant reactions. Bowers et al. (2013) measured the 33S(α,p)36Cl cross section at various energies in the range of 0.70-2.42 MeV/A, and found them to be systematically under predicted by Hauser-Feshbach statistical model codes TALYS and NON-SMOKER, highlighting the need for more empirical data for these cross sections. Recent results of the re-measurement of the 33S(α,p)36Cl reaction, providing greater coverage of the same energy range as Bowers et al., will be presented. Future plans for measurement of other 36Cl producing reactions will also be discussed.

  6. Computational analysis of the mechanism of chemical reactions in terms of reaction phases: hidden intermediates and hidden transition States.

    Kraka, Elfi; Cremer, Dieter


    Computational approaches to understanding chemical reaction mechanisms generally begin by establishing the relative energies of the starting materials, transition state, and products, that is, the stationary points on the potential energy surface of the reaction complex. Examining the intervening species via the intrinsic reaction coordinate (IRC) offers further insight into the fate of the reactants by delineating, step-by-step, the energetics involved along the reaction path between the stationary states. For a detailed analysis of the mechanism and dynamics of a chemical reaction, the reaction path Hamiltonian (RPH) and the united reaction valley approach (URVA) are an efficient combination. The chemical conversion of the reaction complex is reflected by the changes in the reaction path direction t(s) and reaction path curvature k(s), both expressed as a function of the path length s. This information can be used to partition the reaction path, and by this the reaction mechanism, of a chemical reaction into reaction phases describing chemically relevant changes of the reaction complex: (i) a contact phase characterized by van der Waals interactions, (ii) a preparation phase, in which the reactants prepare for the chemical processes, (iii) one or more transition state phases, in which the chemical processes of bond cleavage and bond formation take place, (iv) a product adjustment phase, and (v) a separation phase. In this Account, we examine mechanistic analysis with URVA in detail, focusing on recent theoretical insights (with a variety of reaction types) from our laboratories. Through the utilization of the concept of localized adiabatic vibrational modes that are associated with the internal coordinates, q(n)(s), of the reaction complex, the chemical character of each reaction phase can be identified via the adiabatic curvature coupling coefficients, A(n,s)(s). These quantities reveal whether a local adiabatic vibrational mode supports (A(n,s) > 0) or resists

  7. Insights into the mechanism of the reaction between hydrogen sulfide and peroxynitrite.

    Cuevasanta, Ernesto; Zeida, Ari; Carballal, Sebastián; Wedmann, Rudolf; Morzan, Uriel N; Trujillo, Madia; Radi, Rafael; Estrin, Darío A; Filipovic, Milos R; Alvarez, Beatriz


    Hydrogen sulfide and peroxynitrite are endogenously generated molecules that participate in biologically relevant pathways. A revision of the kinetic features of the reaction between peroxynitrite and hydrogen sulfide revealed a complex process. The rate constant of peroxynitrite decay, (6.65 ± 0.08) × 10(3) M(-1) s(-1) in 0.05 M sodium phosphate buffer (pH 7.4, 37°C), was affected by the concentration of buffer. Theoretical modeling suggested that, as in the case of thiols, the reaction is initiated by the nucleophilic attack of HS(-) on the peroxide group of ONOOH by a typical bimolecular nucleophilic substitution, yielding HSOH and NO2(-). In contrast to thiols, the reaction then proceeds to the formation of distinct products that absorb near 408 nm. Experiments in the presence of scavengers and carbon dioxide showed that free radicals are unlikely to be involved in the formation of these products. The results are consistent with product formation involving the reactive intermediate HSSH and its fast reaction with a second peroxynitrite molecule. Mass spectrometry and UV-Vis absorption spectra predictions suggest that at least one of the products is HSNO2 or its isomer HSONO.

  8. Reaction kinetics of polybutylene terephthalate polycondensation reaction

    Darda, P. J.; Hogendoorn, J. A.; Versteeg, G. F.; Souren, F.


    The kinetics of the forward polycondensation reaction of polybutylene terephthalate (PBT) has been investigated using thermogravimetric analysis (TGA). PBT - prepolymer with an initial degree of polymerization of 5.5 was used as starting material. The PBT prepolymer was prepared from dimethyl tereph

  9. Transfusion reaction - hemolytic

    ... of allergic transfusion reactions that do not cause hemolysis. ... transfusion, the transfusion must be stopped right away. Blood samples from the recipient (person getting the transfusion) and ...

  10. Desosamine in multicomponent reactions

    Achatz, Sepp; Dömling, Alexander


    Desosamine occurring ubiquitously in natural products is introduced into isocyanide based multicomponent reaction chemistry. Corresponding products are of potential interest for the design of novel antibiotics. © 2006.

  11. Metal-mullite reactions

    Loehman, R.E. [Sandia National Labs., Albuquerque, NM (United States); Tomsia, A.P. [Pask Research and Engineering, Berkeley, CA (United States)


    Mullite was reacted with pure Al and with Ti or Zr dissolved in Ag-Cu eutectic alloys at 1100 C in Ar. Analysis of the Ti and Zr-containing specimens showed reaction zones with compositions of Ti{sub 50}Cu{sub 3O}O{sub 20} and ZrO{sub 2}, respectively. The Al-mullite specimen showed much more extensive penetration into the ceramic and a more diffuse reaction zone than the other two systems. Al{sub 2}O{sub 3} and Si were the main reaction products for Al-mullite reaction.

  12. Reactions at Solid Surfaces

    Ertl, Gerhard


    Expanding on the ideas first presented in Gerhard Ertl's acclaimed Baker Lectures at Cornell University, Reactions at Solid Surfaces comprises an authoritative, self-contained, book-length introduction to surface reactions for both professional chemists and students alike. Outlining our present understanding of the fundamental processes underlying reactions at solid surfaces, the book provides the reader with a complete view of how chemistry works at surfaces, and how to understand and probe the dynamics of surface reactions. Comparing traditional surface probes with more modern ones, and brin

  13. Desosamine in multicomponent reactions

    Achatz, Sepp; Dömling, Alexander


    Desosamine occurring ubiquitously in natural products is introduced into isocyanide based multicomponent reaction chemistry. Corresponding products are of potential interest for the design of novel antibiotics. © 2006.

  14. [The relevance of Choukroun's Platelet-Rich Fibrin (PRF) during middle ear surgery: preliminary results].

    Braccini, F; Tardivet, L; Dohan Ehrenfest, D M


    To evaluate the relevance of Leucocyte- and Platelet-Rich Fibrin (L-PRF, Choukroun's technique) Concentrates during tympanoplasty. 152 myringoplasties (including 2 cases with bilateral tympanic perforations) were treated by the senior surgeon in 150 patients, 63 women and 87 males aged between 25 and 55-years-old, between december 2004 and june 2008. These patients showed non marginal tympanic perforations, sized from punctiform to subtotal. For the smallest perforations, a PRF cylinder was used alone to fill the perforation without preparing a tympanomeatus flap (Champagne plug technique). For perforations largest than the third of the tympanic surface, temporal aponeurosis graft in underlay was preferred, and optimized by the lateral application of a PRF membrane (hamburger technique). 6 failures were recorded in this case series, with tympans showing residual microperforations, after a minimum follow-up of 6 months. The success rate was thus close to 96%. The mean success rate without PRF is normally 85%. All failures were recorded on large non marginal lesions. PRF will never save an inadequate surgical procedure, but it offers both mechanical and inflammatory protection to the tympanic graft and accelerates cell proliferation and matrix remodelling. Moreover, this autologous biomaterial induces no undesirable tissue reaction, is easy, quick and cheap to produce and is easily manipulated during the surgical procedure. It seems a precious help for the otologist, in order to improve tympanic healing. PRF potential applications in the middle-ear surgery seem numerous.

  15. Metformin exposure at environmentally relevant concentrations causes potential endocrine disruption in adult male fish

    Pharmaceuticals and personal care products (PPCPs) are emerging contaminants that have been found ubiquitously in wastewater and surface waters around the world. A major source of these compounds is incomplete metabolism in humans and subsequent excretion in human waste. PPCPs th...

  16. Concentrations of undeclared allergens in food products can reach levels that are relevant for public health

    Spanjersberg, M. Q. I.; Knulst, A. C.; Kruizinga, A. G.; Van Duijn, G.; Houben, G. F.


    Food products can become contaminated with food allergens due to cross-contact. Precautionary 'may contain' labelling may alert to the possible presence of an allergen, but guidance for such labelling is lacking. As a result, allergy information on the packaging may not be reliable and allergic cons

  17. Biphasic modulation of cell proliferation by quercetin at concentrations physiologically relevant in humans

    Woude, van der H.; Gliszczynska-Swiglo, A.; Struijs, K.; Smeets, A.; Alink, G.M.; Rietjens, I.M.C.M.


    Optimal in vitro conditions regarding quercetin solubility and stability were defined. Using these conditions, the effect of quercetin on proliferation of the colon carcinoma cell lines HCT-116 and HT29 and the mammary adenocarcinoma cell line MCF-7 was investigated. For the colon carcinoma cell lin


    Ion-exchange chromatography is the most often used analytical approach for arsenicspeciation, due to the weak-acid nature of several of its species. However, no singletechnique can determine all potentially occurring arsenic species, especially in complexe...

  19. Metformin exposure at environmentally relevant concentrations causes potential endocrine disruption in adult male fish

    Pharmaceuticals and personal care products (PPCPs) are emerging contaminants that have been found ubiquitously in wastewater and surface waters around the world. A major source of these compounds is incomplete metabolism in humans and subsequent excretion in human waste. PPCPs th...

  20. Concentrations of undeclared allergens in food products can reach levels that are relevant for public health

    Spanjersberg, M. Q. I.; Knulst, A. C.; Kruizinga, A. G.; Van Duijn, G.; Houben, G. F.


    Food products can become contaminated with food allergens due to cross-contact. Precautionary 'may contain' labelling may alert to the possible presence of an allergen, but guidance for such labelling is lacking. As a result, allergy information on the packaging may not be reliable and allergic cons

  1. Cytotoxic evaluation of a mixture of eight pollutants at environmental relevant concentrations

    JM, Pérez Martín


    Full Text Available La presencia ubicua de contaminantes ambientales y la adecuada evaluación de su riesgo potencial para la salud humana y ambiental es un área de gran preocupación. En este trabajo se ha simulado un escenario in vitro de exposición a largo plazo de una mezcla de ocho contaminantes a concentraciones reales presentes en el medio ambiente, utilizando la línea celular de mamífero Vero. Nuestros resultados demuestran que se alteran significativamente las tasas de proliferación celular, ya sea por estimulación o inhibición, dependiendo de la composición de la mezcla y del tiempo de exposición. En vista de estos resultados, recalcamos la necesidad de revisar los niveles de seguridad aceptados por las agencias reguladoras para contaminantes emergentes, teniendo en cuenta que las mezclas de contaminantes representan una amenaza para la salud humana y medioambiental.

  2. Red-light initiated atmospheric reactions of vibrationally excited molecules.

    Vaida, V; Donaldson, D J


    We present a brief review of long wavelength, red-light initiated chemistry from excited vibrational levels of the ground electronic state of atmospheric trace species. When sunlight driven electronic state reactions are not effective, photochemical processes occurring by vibrational overtone excitation have been found to be important in reactions of oxidized atmospheric compounds (acids, alcohols and peroxides) prevalent in the Earth's atmosphere. This review focuses on the fundamental energetic, mechanistic and dynamical aspects of unimolecular reactions of vibrationally excited atmospheric species. We will discuss the relevance of these red light initiated reactions to address the discrepancies between atmospheric measurements and results of standard atmospheric models.

  3. Relevant Perturbation of Entanglement Entropy and Stationarity

    Nishioka, Tatsuma


    A relevant perturbation of the entanglement entropy of a sphere is examined holographically near the UV fixed point. Varying the conformal dimension of the relevant operator, we obtain three different sectors: 1) the entanglement entropy is stationary and the perturbative expansion is well-defined with respect to the relevant coupling, 2) the entropy is stationary, but the perturbation fails, 3) the entropy is neither stationary nor perturbative. We compare our holographic results with the numerical calculation for a free massive scalar field in three-dimensions, and find a qualitative agreement between them. We argue that these statements hold for any relevant perturbation in any quantum field theory invariant under the Poincare symmetry.

  4. Interactions of Pellet with Reactor Relevant Plasma

    PENGLilin; DENGBaiquan; YANJiancheng


    Extended algorithm has been developed for ablation rate calculations of Li, Be, B impurity pellets and five combinations of solid isotopic hydrogenic H2, HD, D2, DT, T2 pellets. Numerical calculations have been performed for reactor relevant plasma.

  5. The foundation of the concept of relevance

    Hjørland, Birger


    be termed “the epistemological view”). The concept of relevance, like other basic concepts, is influenced by overall approaches to information science, such as the cognitive view and the domain-analytic view. There is today a trend toward a social paradigm for information science. This paper offers...... that what was regarded as the most fundamental view by Saracevic in 1975 has not since been considered (with very few exceptions). Other views, which are based on less fruitful assumptions, have dominated the discourse on relevance in information retrieval and information science. Many authors have...... reexamined the concept of relevance in information science, but have neglected the subject knowledge view, hence basic theoretical assumptions seem not to have been properly addressed. It is as urgent now as it was in 1975 seriously to consider “the subject knowledge view” of relevance (which may also...

  6. Interpersonal communication: It's relevance to nursing practice ...

    Interpersonal communication: It's relevance to nursing practice. ... of the dynamic relationship between clients' potentiality to perceive and be understood ... understanding the needs of the patients and planning effective intervention for meeting ...



    philosophy has come to be perceived as having enjoyed its relevance in the past and ... students of philosophy do not understand what philosophy students do in their philosophy ..... interpersonal, inter-ethnic and international relationships.

  8. Acceleration and Reaction Mechanism of the N-Nitrosation Reaction of Dimethylamine with Nitrite in Ice.

    Kitada, Kodai; Suda, Yusuke; Takenaka, Norimichi


    Some reactions (e.g., oxidation of nitrite, denitrification of ammonium) are accelerated in freeze-concentrated solution (FCS) compared to those in aqueous solution. Ice is highly intolerant to impurities, and the ice excludes those that would accelerate reactions. Here we show the acceleration of the N-nitrosation reaction of dimethylamine (DMA) with nitrite to produce N-nitrosodimethylamine (NDMA) in FCS. NDMA is a carcinogenic compound, and this reaction is potentially accelerated in frozen fish/meat. The eaction rate of the N-nitrosation reaction becomes fastest at specific pH. This means that it is a third-order reaction. Theoretical pH values of the peak in the third-order reaction are higher than the experimental one. Freeze-concentration of acidic solution causes pH decrement; however, the freeze-concentration alone could not explain the difference of pH values. The theoretical value was obtained under the assumption that no solute took part in ice. However, solutes are incorporated in ice with a small distribution coefficient of solutes into ice. This small incorporation enhanced the decrement of pH values. Using the distribution coefficient of chloride and sodium ion and assuming those of nitrite and DMA to explain the enhancement, we succeeded in estimating the distribution coefficients of nitrite: 2 × 10(-3) and DMA: 3 × 10(-2).


    How, Zuo Tong; Linge, Kathryn; Busetti, Francesco; Joll, Cynthia A


    Chlorination of amino acids can result in the formation of organic monochloramines or organic dichloramines, depending on the chlorine to amino acid ratio (Cl:AA). After formation, organic chloramines degrade into aldehydes, nitriles and N-chloraldimines. In this paper, the formation of organic chloramines from chlorination of lysine, tyrosine and valine were investigated. Chlorination of tyrosine and lysine demonstrated that the presence of a reactive secondary group can increase the Cl:AA ratio required for the formation of N,N-dichloramines, and potentially alter the reaction pathways between chlorine and amino acids, resulting in the formation of unexpected by-products. In a detailed investigation, we report rate constants for all reactions in the chlorination of valine, for the first time, using experimental results and modelling. At Cl:AA = 2.8, the chlorine was found to first react quickly with valine (5.4x104 M-1 s-1) to form N-monochlorovaline, with a slower subsequent reaction with N-monochlorovaline to form N,N-dichlorovaline (4.9x102 M-1 s-1), although some N-monochlorovaline degraded into isobutyraldehyde (1.0x10-4 s-1). The N,N-dichlorovaline then competitively degraded into isobutyronitrile (1.3x10-4 s-1) and N-chloroisobutyraldimine (1.2x10-4 s-1). In conventional drinking water disinfection, N-chloroisobutyraldimine can potentially be formed in concentrations higher than its odour threshold concentration, resulting in aesthetic challenges and an unknown health risk.

  10. Individual differences in defensive stress-responses: The potential relevance for psychopathology

    Niermann, H.C.M.; Figner, B.; Roelofs, K.


    Alterations in primary freeze and fight-or-flight reactions in animals have been associated with increased vulnerability to develop anxious or aggressive symptomatology. Despite the potential relevance of these primary defensive responses for human stress-coping, they are still largely unexplored in

  11. Advances in lipase-catalyzed esterification reactions.

    Stergiou, Panagiota-Yiolanda; Foukis, Athanasios; Filippou, Michalis; Koukouritaki, Maria; Parapouli, Maria; Theodorou, Leonidas G; Hatziloukas, Efstathios; Afendra, Amalia; Pandey, Ashok; Papamichael, Emmanuel M


    Lipase-catalyzed esterification reactions are among the most significant chemical and biochemical processes of industrial relevance. Lipases catalyze hydrolysis as well as esterification reactions. Enzyme-catalyzed esterification has acquired increasing attention in many applications, due to the significance of the derived products. More specifically, the lipase-catalyzed esterification reactions attracted research interest during the past decade, due to an increased use of organic esters in biotechnology and the chemical industry. Lipases, as hydrolyzing agents are active in environments, which contain a minimum of two distinct phases, where all reactants are partitioned between these phases, although their distribution is not fixed and changes as the reaction proceeds. The kinetics of the lipase-catalyzed reactions is governed by a number of factors. This article presents a thorough and descriptive evaluation of the applied trends and perspectives concerning the enzymatic esterification, mainly for biofuel production; an emphasis is given on essential factors, which affect the lipase-catalyzed esterification reaction. Moreover, the art of using bacterial and/or fungal strains for whole cell biocatalysis purposes, as well as carrying out catalysis by various forms of purified lipases from bacterial and fungal sources is also reviewed.

  12. Cascade reactions catalyzed by metal organic frameworks.

    Dhakshinamoorthy, Amarajothi; Garcia, Hermenegildo


    Cascade or tandem reactions where two or more individual reactions are carried out in one pot constitute a clear example of process intensification, targeting the maximization of spatial and temporal productivity with mobilization of minimum resources. In the case of catalytic reactions, cascade processes require bi-/multifunctional catalysts that contain different classes of active sites. Herein, we show that the features and properties of metal-organic frameworks (MOFs) make these solids very appropriate materials for the development of catalysts for cascade reactions. Due to composition and structure, MOFs can incorporate different types of sites at the metal nodes, organic linkers, or at the empty internal pores, allowing the flexible design and synthesis of multifunctional catalysts. After some introductory sections on the relevance of cascade reactions from the point of view of competitiveness, sustainability, and environmental friendliness, the main part of the text provides a comprehensive review of the literature reporting the use of MOFs as heterogeneous catalysts for cascade reactions including those that combine in different ways acid/base, oxidation/reduction, and metal-organic centers. The final section summarizes the current state of the art, indicating that the development of a first commercial synthesis of a high-added-value fine chemical will be a crucial milestone in this area.

  13. Reaction cycle and thermodynamics in bacteriorhodopsin

    Lanyi, J. K.


    Light causes the all-trans to 13-cis isomerization of the retinal in bacteriorhodopsin; the thermal relaxation leading back to the initial state drives proton transport first via proton transfer between the retinal Schiff base and D85 and then between the Schiff base and D96. The reaction sequence and thermodynamics of this photocycle are described by measuring time-resolved absorption changes with a gated multichannel analyzer between 100 ns and 100 ms, at six temperatures between 5 degrees C and 30 degrees C. Analysis of the energetics of the chromophore reaction sequence is on the basis of a recently proposed model (Varo & Lanyi, Biochemistry 30, 5016-5022, 1991) which consists of a single cycle and many reversible reactions: BR -hv-->KLM1-->M2NO-->BR. The existence of the M1-->M2 reaction, which functions as the switch in the proton transfer, is confirmed by spectroscopic evidence. The calculated thermodynamic parameters indicate that the exchange of free energy between the protein and the protons is at the switch step. Further, a large entropy decrease at this reaction suggests a protein conformation change which will conserve delta G for driving the completion of the reaction cycle. The results provide insights to mechanism and energy coupling in this system, with possible relevance to the general question of how ion pumps function.

  14. Neutrino reactions in hot and dense matter

    Lohs, Andreas


    In this thesis, neutrino reactions in hot and dense matter are studied. In particular, this work is concerned with neutrino-matter interactions that are relevant for neutrino transport in core-collapse supernovae (CCSNe). The majority of the energy from a CCSN is released in the form of neutrinos. Accurate understanding and computation of these interactions is most relevant to achieve sufficiently reliable predictions for the evolution of CCSNe and other related question such as the production of heavy elements or neutrino oscillations. For this purpose this work follows the combined approach of searching for new important neutrino reactions and improving the computation of those reactions that are already implemented. First we estimate the relevance of charged-current weak interactions that include muon-neutrinos or muons, as well as the role of neutron decay for neutrino transport in CCSNe. All of these reactions were previously neglected in CCSN-simulations. We derive and compute the matrix element and subsequent semi-analytic expressions for transport properties like the inverse mean free path of the new reactions. It is found that these reactions are important for muon neutrinos and low energy electron antineutrinos at very high densities in the protoneutron star surface. Consequently their implementation might lead to several changes in the prediction of CCSNe signatures such as the nucleosynthesis yields. Second we improve the precision in the computation of well known neutrino-nucleon reactions like neutrino absorption on neutrons. We derive semi-analytic expressions for transport properties that use less restrictive approximations while keeping the computational demand constant. Therefore we consider the full relativistic kinematics of all participating particles i.e. allowing for relativistic nucleons and finite lepton masses. Also the weak magnetism terms of the matrix elements are explicitly included to all orders. From our results we suggest that the

  15. Fluorogenic organocatalytic reactions

    Raeisolsadati Oskouei, M.


    In this thesis, we introduce fluorescence spectroscopy as a new tool to gain insight into the interactions between the substrates and catalyst during organocatalytic reactions. The ultimate goal is to resolve the kinetics of the binding and reaction steps and obtain detailed understanding of the

  16. Chemical burn or reaction

    ... this page: // Chemical burn or reaction To use the sharing features on this page, please enable JavaScript. Chemicals that touch skin can lead to a reaction on the skin, throughout the body, or both. ...

  17. Reactions to Attitudinal Deviancy.

    Levine, John M.; Allen, Vernon L.

    This paper presents a critical review of empirical and theoretical treatments of group reaction to attitudinal deviancy. Inspired by Festinger's (1950) ideas on resolution of attitudinal discrepancies in groups, Schachter (1951) conducted an experiment that has greatly influenced subsequent research and theory concerning reaction to attitudinal…

  18. Allergic reactions to vaccines.

    Wood, Robert A


    Anaphylactic reactions to vaccines are rare but do occur, and have been reported for nearly every vaccine. And while the reaction rate per each dose of vaccine is low, this is a common clinical question due in large part to the enormous numbers of vaccines administered. Reactions are most often due to vaccine constituents rather than the microbial components of the vaccine, but in many instances, the specific ingredient triggering the reaction cannot be definitively identified. Evaluation of patients with suspected vaccine reactions should begin by determining whether the symptoms and timing of the reaction were consistent with a true allergic reaction, followed by an assessment to determine whether the patient needs further doses of the vaccine in question, or similar vaccines, in the future. Skin and serologic testing to vaccines and vaccine constituents can then be performed to further assess the potential cause of the reaction and to develop a plan for future immunizations. Specific guidelines for the administration of influenza vaccines to egg allergic patients have been revised to allow virtually all patients to receive this vaccine in a straightforward manner. © 2013 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  19. Efecto de la concentración de SO2 en las reacciones de calcinación y sulfatación de calcáreos en reactores de lecho fluidizado. // Effect of the SO2 concentration in the calcinations and sulfatation reactions in a fluidized bed reactor.

    J. E. Lindo Samaniego


    Full Text Available Fue realizado un estudio sobre el efecto de las concentraciones de SO2 en la absorción por calcáreo en hornos de LechoFluidizado. Para observar la influencia del SO2 en los parámetros de diferentes procesos físicos y químicos fueron creadosambientes para cuatro concentraciones diferentes de SO2 : 500, 1000, 2000 y 4000 ppm. Se utilizaron dos tipos decalcáreos: Dolimitico-DP y el Calcítico-CI. El Lecho Fluidizado Burbujeante utilizado tiene 160 mm de diámetro interno yfue fluidizado con aire a la temperatura de 850 °C, con una concentración de SO2 deseada. Como material del lecho fueutilizada la arena de cuarzo (99,9% con diámetro de 385 μm y de masa aproximadamente 3,0 kg. El calcáreo fueadicionado en dosificación de 50 g con el reactor ya pre-calentado. Las variaciones de las concentraciones de SO2, CO2,CO, O2 y las descargas, fueron monitoreadas continuamente a la salida del ciclón que fue utilizado para la retención de lapartícula fina. Para esos dados se desarrolló un programa en LabView. El modelo matemático escogido posibilitó ladeterminación de la conversión.Palabras claves: Lecho fluidizado, dióxido de azufre, absorción de azufre, calcáreo , reactor de lechofluidizado.___________________________________________________________________________Abstract.A Study of the effect of the concentrations of SO2 in its absorption by limestones in fluidized bed furnaces wasconducted. For the determination of the SO2 influence on the different physical and chemical parameters of process,such as calcinations and sulfatation four different atmospheres were used in the reator with concentrations of SO2 of500, 1000, 2000 and 4000 ppm. Two types of limestones were used: Dolomite-DP and Calcitic-CI. The bench scalebubbling fluidized bed reactor had a 160 mm internal diameter and was fluidized with air at 850 °C containing therequired concentration of SO2. Bed material was quartz sand (99,9% , with 385 μm diameter and approximately

  20. Chemical reaction and separation method

    Jansen, J.C.; Kapteijn, F.; Strous, S.A.


    The invention is directed to process for performing a chemical reaction in a reaction mixture, which reaction produces water as by-product, wherein the reaction mixture is in contact with a hydroxy sodalite membrane, through which water produced during the reaction is removed from the reaction mixtu

  1. City scale pollen concentration variability

    van der Molen, Michiel; van Vliet, Arnold; Krol, Maarten


    Pollen are emitted in the atmosphere both in the country-side and in cities. Yet the majority of the population is exposed to pollen in cities. Allergic reactions may be induced by short-term exposure to pollen. This raises the question how variable pollen concentration in cities are in temporally and spatially, and how much of the pollen in cities are actually produced in the urban region itself. We built a high resolution (1 × 1 km) pollen dispersion model based on WRF-Chem to study a city's pollen budget and the spatial and temporal variability in concentration. It shows that the concentrations are highly variable, as a result of source distribution, wind direction and boundary layer mixing, as well as the release rate as a function of temperature, turbulence intensity and humidity. Hay Fever Forecasts based on such high resolution emission and physical dispersion modelling surpass traditional hay fever warning methods based on temperature sum methods. The model gives new insights in concentration variability, personal and community level exposure and prevention. The model will be developped into a new forecast tool to serve allergic people to minimize their exposure and reduce nuisance, coast of medication and sick leave. This is an innovative approach in hay fever warning systems.

  2. Reaction products of chlorine dioxide.

    Stevens, A A


    Inspection of the available literature reveals that a detailed investigation of the aqueous organic chemistry of chlorine dioxide and systematic identification of products formed during water disinfection has not been considered. This must be done before an informed assessment can be made of the relative safety of using chlorine dioxide as a disinfectant alternative to chlorine. Although trihalomethanes are generally not formed by the action of chlorine dioxide, the products of chlorine dioxide treatment of organic materials are oxidized species, some of which also contain chlorine. The relative amounts of species types may depend on the amount of chlorine dioxide residual maintained and the concentration and nature of the organic material present in the source water. The trend toward lower concentrations of chlorinated by-products with increasing ClO2 concentration, which was observed with phenols, has not been observed with natural humic materials as measured by the organic halogen parameter. Organic halogen concentrations have been shown to increase with increasing chlorine dioxide dose, but are much lower than those observed when chlorine is applied. Aldehydes have been detected as apparent by-products of chlorine dioxide oxidation reactions in a surface water that is a drinking water source. Some other nonchlorinated products of chlorine dioxide treatment may be quinones and epoxides. The extent of formation of these moieties within the macromolecular humic structure is also still unknown. PMID:7151750

  3. Abundances in Astrophysical Environments: Reaction Network Simulations with Reaction Rates from Many-nucleon Modeling

    Amason, Charlee; Dreyfuss, Alison; Launey, Kristina; Draayer, Jerry


    We use the ab initio (first-principle) symmetry-adapted no-core shell model (SA-NCSM) to calculate reaction rates of significance to type I X-ray burst nucleosynthesis. We consider the 18O(p,γ)19F reaction, which may influence the production of fluorine, as well as the 16O(α,γ)20Ne reaction, which is key to understanding the production of heavier elements in the universe. Results are compared to those obtained in the no-core sympletic shell model (NCSpM) with a schematic interaction. We discuss how these reaction rates affect the relevant elemental abundances. We thank the NSF for supporting this work through the REU Site in Physics & Astronomy (NSF grant #1560212) at Louisiana State University. This work was also supported by the U.S. NSF (OCI-0904874, ACI -1516338) and the U.S. DOE (DE-SC0005248).

  4. Environmentally relevant impacts of nano-TiO2 on abiotic degradation of bisphenol A under sunlight irradiation.

    Wu, Wei; Shan, Guoqiang; Wang, Shanfeng; Zhu, Lingyan; Yue, Longfei; Xiang, Qian; Zhang, Yinqing; Li, Zhuo


    Understanding the effects of nano-TiO2 particles on the environmental behaviors of organic pollutants in natural aquatic environments is of paramount importance considering that large amount of nano-TiO2 is being released in the environment. In this study, the effect of nano-TiO2 on the degradation of bisphenol A (BPA) in water was investigated under simulated solar light irradiation. The results indicated that nano-TiO2 at environmentally relevant concentration (1 mg/L) could significantly facilitate the abiotic degradation of BPA (also at low concentration) under mild solar light irradiation, with the pseudo first-order rate constant (kobs) for BPA degradation raised by 1-2 orders of magnitude. As reflected by the inhibition experiments, hydroxyl radicals (OHs) and superoxide radical species were the predominant active species responsible for BPA degradation. The reaction was affected by water pH, and the degradation rate was higher at acidic or alkaline conditions than that at neutral condition. Humic acid (HA) also affected the reaction rate, depending on its concentration. At lower concentration (the mass ratio of HA/nano-TiO2 was 0.1:1), HA improved the dispersion and stability of nano-TiO2 in aquatic environment. As a result, the yield of OHs by nano-TiO2 under sunlight irradiation increased and BPA degradation was facilitated. When the HA concentration increased, a coating of HA formed on the surface of nano-TiO2. Although nano-TiO2 became more stable, the light absorption by nano-TiO2 was significantly reduced due to the strong light absorption of the HA coated on the surface. As a consequence, the yield of OH decreased and BPA degradation was depressed. The results imply that nano-TiO2 at low concentration may distinctly mediate BPA degradation, and can contribute to the natural attenuation of some organic pollutants in aquatic environment with low level of HA. However, this process would be significantly reduced in the presence of high level of HA.

  5. High Energy Density Plasmas (HEDP) for studies of basic nuclear science relevant to Stellar and Big Bang Nucleosynthesis

    Frenje, Johan


    Thermonuclear reaction rates and nuclear processes have been explored traditionally by means of conventional accelerator experiments, which are difficult to execute at conditions relevant to stellar nucleosynthesis. Thus, nuclear reactions at stellar energies are often studied through extrapolations from higher-energy data or in low-background underground experiments. Even when measurements are possible using accelerators at relevant energies, thermonuclear reaction rates in stars are inherently different from those in accelerator experiments. The fusing nuclei are surrounded by bound electrons in accelerator experiments, whereas electrons occupy mainly continuum states in a stellar environment. Nuclear astrophysics research will therefore benefit from an enlarged toolkit for studies of nuclear reactions. In this presentation, we report on the first use of High Energy Density Plasmas for studies of nuclear reactions relevant to basic nuclear science, stellar and Big Bang nucleosynthesis. These experiments were carried out at the OMEGA laser facility at University of Rochester and the National Ignition Facility (NIF) at Lawrence Livermore National Laboratory, in which spherical capsules were irradiated with powerful lasers to compress and heat the fuel to high enough temperatures and densities for nuclear reactions to occur. Four experiments will be highlighted in this presentation. In the first experiment, the differential cross section for the elastic neutron-triton (n-T) scattering at 14.1 MeV was measured with significantly higher accuracy than achieved in accelerator experiments. In the second experiment, the T(t,2n)4He reaction, a mirror reaction to the 3He(3He,2p)4He reaction that plays an important role in the proton-proton chain that transforms hydrogen into ordinary 4He in stars like our Sun, was studied at energies in the range 15-40 keV. In the third experiment, the 3He+3He solar fusion reaction was studied directly, and in the fourth experiment, we

  6. Photocatalytic silver enhancement reaction for gravimetric immunosensors.

    Seo, Hyejung; Joo, Jinmyoung; Ko, Wooree; Jung, Namchul; Jeon, Sangmin


    A novel microgravimetric immunosensor has been developed using TiO(2) nanoparticle-modified immunoassay and silver enhancement reaction. An antibody-conjugated TiO(2) nanoparticle is bound to the AFP antigen immobilized on a quartz resonator. When the nanoparticles are exposed to UV light in a silver nitrate solution, the photocatalytic reduction of silver ions results in the formation of metallic silver onto the nanoparticles and induces a decrease in the resonance frequency. The frequency change by this photocatalytic reduction reaction is three orders of magnitude larger than the change by antigen binding alone. The efficiency of the photocatalytic reaction has been found to increase with the fraction of anatase crystallites in the nanoparticles and the concentration of the AgNO(3) solution. The results highlight the potential of the photocatalytic nanoparticles for the detection of low concentrations of target molecules using gravimetric sensors.

  7. Direct Imaging of Nanoscale Dissolution of Dicalcium Phosphate Dihydrate by an Organic Ligand: Concentration Matters

    Qin, Lihong [Huazhong Agricultural University, China; Zhang, Wenjun [Huazhong Agricultural University, China; Lu, Jianwei [Huazhong Agricultural University, China; Stack, Andrew G [ORNL; Wang, Lijun [Huazhong Agricultural University, China


    Unraveling the kinetics and mechanisms of sparingly soluble calcium orthophosphate (Ca!P) dissolution in the presence of organic acids at microscopic levels is important for an improved understanding in determining the effectiveness of organic acids present in most rhizosphere environments. Herein, we use in situ atomic force microscopy (AFM) coupled with a fluid reaction cell to image dissolution on the (010) face of brushite, CaHPO4 2H2O, in citrate- bearing solutions over a broad concentration range. We directly measure the dependence of molecular step retreat rate on citrate concentration at various pH values and ionic strengths, relevant to soil solution conditions. We find that low concentrations of citrate(10!100 M)inducedareductioninstepretreatratesalongboththe[10 0]Ccand[101] Ccdirections.However,at higher concentrations (exceeding 0.1 mM), this inhibitory effect was reversed with step retreat speeds increasing rapidly. These results demonstrate that the concentration-dependent modulation of nanoscale Ca!P phase dissolution by citrate may be applied to analyze the controversial role of organic acids in enhancing Ca!P mineral dissolution in a more complex rhizosphere environment. These in situ observations may contribute to resolving the previously unrecognized interactions of root exudates (low molecular weight organic acids) and sparingly soluble Ca!P minerals.

  8. Direct imaging of nanoscale dissolution of dicalcium phosphate dihydrate by an organic ligand: concentration matters.

    Qin, Lihong; Zhang, Wenjun; Lu, Jianwei; Stack, Andrew G; Wang, Lijun


    Unraveling the kinetics and mechanisms of sparingly soluble calcium orthophosphate (Ca-P) dissolution in the presence of organic acids at microscopic levels is important for an improved understanding in determining the effectiveness of organic acids present in most rhizosphere environments. Herein, we use in situ atomic force microscopy (AFM) coupled with a fluid reaction cell to image dissolution on the (010) face of brushite, CaHPO4 · 2H2O, in citrate-bearing solutions over a broad concentration range. We directly measure the dependence of molecular step retreat rate on citrate concentration at various pH values and ionic strengths, relevant to soil solution conditions. We find that low concentrations of citrate (10-100 μM) induced a reduction in step retreat rates along both the [100]Cc and [101]Cc directions. However, at higher concentrations (exceeding 0.1 mM), this inhibitory effect was reversed with step retreat speeds increasing rapidly. These results demonstrate that the concentration-dependent modulation of nanoscale Ca-P phase dissolution by citrate may be applied to analyze the controversial role of organic acids in enhancing Ca-P mineral dissolution in a more complex rhizosphere environment. These in situ observations may contribute to resolving the previously unrecognized interactions of root exudates (low molecular weight organic acids) and sparingly soluble Ca-P minerals.

  9. Transport—Reaction Process in the Reaction of Flue Gas Desulfurization

    YanYan; DuuJongLee; 等


    A theoreticasl investigation was conducted to study the transport-reaction process in the spray-drying flue gas desulfurization.A transport-reaction model of single particle was proposed,which considered the water evaporation from the surface of droplet and the reaction at the same time.BHased on this model,the reaction rate and t6he absorbent utilization can be calculated.The most appropriate particle radius and the initial absorbent concentration can be deduced through comparing the wet lifetime with the residence time,the result shows in the case that the partial pressure of vapor in the bulk flue gas is 2000Pa,the optimum initial radius and absorent concentration are 210-310μm and 23% respectively.The model can supply the optimum parameters for semi-dry FGD system designed.

  10. Task relevance effects in electrophysiological brain activity: early, but not first.

    Fellrath, Julia; Manuel, Aurélie L; Ptak, Radek


    A current controversy surrounds the question whether high-level features of a stimulus such as its relevance to the current task may affect early attentional processes. According to one view abruptly appearing stimuli gain priority during an initial feedforward processing stage and therefore capture attention even if they are irrelevant to the task. Alternatively, only stimuli that share a relevant property with the target may capture attention of the observer. Here, we used high-density EEG to test whether task relevance may modulate early feedforward brain activity, or whether it only becomes effective once the physical characteristics of the stimulus have been processed. We manipulated task relevance and visual saliency of distracters presented left or right of an upcoming central target. We found that only the relevance of distracters had an effect on manual reaction times to the target. However, the analysis of electrocortical activity revealed three discrete processing stages during which pure effects of distracter saliency (~80-160 ms), followed by an interaction between saliency and relevance (~130-240 ms) and finally pure effects of relevance (~230-370 ms) were observed. Electrical sources of early saliency effects and later relevance effects were localized in the posterior parietal cortex, predominantly over the right hemisphere. These findings support the view that during the initial feedforward stage only physical (bottom-up) factors determine cortical responses to visual stimuli, while top-down effects interfere at later processing stages.

  11. Rethinking "relevance": South African psychology in context.

    Long, Wahbie


    This article examines the phenomenon known as the "relevance debate" in South African psychology. It begins with a historical overview of the contours of the discipline in that country before describing the controversy's international dimensions, namely, the revolutionary politics of 1960s higher education and the subsequent emergence of cognate versions of the debate in American, European, and "Third World" psychology. The article then details how South Africa's "relevance" project enjoyed a special affinity with an assortment of ethnic-cultural, national, and continental myths and metaphors, all of which served the interests of the political formations of the day. It discusses how, in present-day South Africa, the intelligentsia has become an important catalyst for the so-called African Renaissance, which seeks to provide "relevant" solutions for the regeneration of African society. However, the global hegemony of what began in the 1970s as a "second academic revolution," aided by the lifting of the academic boycott of South Africa, has blunted the once critical edge of "relevance" discourse. A new mode of knowledge production now holds sway, the outcome of a dramatic reformulation of the capitalist manifesto in which the values of the "May 68" generation have been hijacked by a managerialist rationality. In light of the capitalization of the knowledge-production enterprise, it is concluded that the idiom of "relevance" has outlived its usefulness.

  12. Studies on Relevance, Ranking and Results Display

    Gelernter, Judith; Carbonell, Jaime


    This study considers the extent to which users with the same query agree as to what is relevant, and how what is considered relevant may translate into a retrieval algorithm and results display. To combine user perceptions of relevance with algorithm rank and to present results, we created a prototype digital library of scholarly literature. We confine studies to one population of scientists (paleontologists), one domain of scholarly scientific articles (paleo-related), and a prototype system (PaleoLit) that we built for the purpose. Based on the principle that users do not pre-suppose answers to a given query but that they will recognize what they want when they see it, our system uses a rules-based algorithm to cluster results into fuzzy categories with three relevance levels. Our system matches at least 1/3 of our participants' relevancy ratings 87% of the time. Our subsequent usability study found that participants trusted our uncertainty labels but did not value our color-coded horizontal results layout ...

  13. Enzyme Reactions in Nanoporous, Picoliter Volume Containers

    Siuti, Piro [ORNL; Retterer, Scott T [ORNL; Choi, Chang Kyoung [Michigan Technological University; Doktycz, Mitchel John [ORNL


    Advancements in nanoscale fabrication allow creation of small volume reaction containers that can facilitate the screening and characterization of enzymes. A porous, ~19 pL volume vessel has been used in this work to carry out enzyme reactions under varying substrate concentrations. Glucose oxidase and horseradish peroxidase can be contained in these structures and diffusively fed with a solution containing glucose and the fluorogenic substrate Amplex Red through the engineered nanoscale pore structure. Fluorescent microscopy was used to monitor the reaction, which was carried out under microfluidic control. Kinetic characteristics of the enzyme were evaluated and compared with results from conventional scale reactions. These picoliter, nanoporous containers can facilitate quick determination of enzyme kinetics in microfluidic systems without the requirement of surface tethering and can be used for applications in drug discovery, clinical diagnostics and high-throughput screening.

  14. The Reaction Wheel Pendulum

    Block, Daniel J; Spong, Mark W


    This monograph describes the Reaction Wheel Pendulum, the newest inverted-pendulum-like device for control education and research. We discuss the history and background of the reaction wheel pendulum and other similar experimental devices. We develop mathematical models of the reaction wheel pendulum in depth, including linear and nonlinear models, and models of the sensors and actuators that are used for feedback control. We treat various aspects of the control problem, from linear control of themotor, to stabilization of the pendulum about an equilibrium configuration using linear control, t

  15. Electron transfer reactions

    Cannon, R D


    Electron Transfer Reactions deals with the mechanisms of electron transfer reactions between metal ions in solution, as well as the electron exchange between atoms or molecules in either the gaseous or solid state. The book is divided into three parts. Part 1 covers the electron transfer between atoms and molecules in the gas state. Part 2 tackles the reaction paths of oxidation states and binuclear intermediates, as well as the mechanisms of electron transfer. Part 3 discusses the theories and models of the electron transfer process; theories and experiments involving bridged electron transfe

  16. How relevant is panallergen sensitization in the development of allergies?

    McKenna, Olivia E; Asam, Claudia; Araujo, Galber R; Roulias, Anargyros; Goulart, Luiz R; Ferreira, Fatima


    Panallergens comprise various protein families of plant as well as animal origin and are responsible for wide IgE cross-reactivity between related and unrelated allergenic sources. Such cross-reactivities include reactions between various pollen sources, pollen and plant-derived foods as well as invertebrate-derived inhalants and foodstuff. Here, we provide an overview on the most clinically relevant panallergens from plants (profilins, polcalcins, non-specific lipid transfer proteins, pathogenesis-related protein family 10 members) and on the prominent animal-derived panallergen family, tropomyosins. In addition, we explore the role of panallergens in the sensitization process and progress of the allergic disease. Emphasis is given on epidemiological aspects of panallergen sensitization and clinical manifestations. Finally, the issues related to diagnosis and therapy of patients sensitized to panallergens are outlined, and the use of panallergens as predictors for cross-reactive allergy and as biomarkers for disease severity is discussed.

  17. Clinical relevance of advanced glycation endproducts for vascular surgery.

    Meerwaldt, R; van der Vaart, M G; van Dam, G M; Tio, R A; Hillebrands, J-L; Smit, A J; Zeebregts, C J


    Atherosclerosis is the main contributor to cardiovascular disease and leads to intimal plaque formation, which may progress to plaque rupture with subsequent thromboembolic events and/or occlusion of the arterial lumen. There is increasing evidence that the development or progression of atherosclerosis is associated with advanced glycation endproducts (AGEs). AGEs are a heterogeneous group of compounds formed by the non-enzymatic reaction of reducing sugars with proteins, lipids, and nucleic acids. An increased understanding of the mechanisms of formation and interaction of AGEs has allowed the development of several potential anti-AGE strategies. This review summarizes AGE formation and biochemistry, the pathogeneic role of AGEs in cardiovascular disease, anti-AGE therapies and clinical relevance to vascular surgery.

  18. Is relevance theory applicable to proverbs’ translation?

    Pegulescu Anca-Mariana


    Full Text Available Translation, viewed as a multi-faceted task, can arise different types of difficulties. Proverbs have been considered special patterns, displaying sometimes hidden meanings or suggesting morals issuing from a particular example. These paremic units - the proverbs - conveyed feelings, states of mind, behaviours or ‘metaphorical descriptions of certain situations’(Krikmann. Starting from Savory’s list of pair-wise contradictory translation principles, I intend to prove that the link between different ‘forms’ and their ‘contents’ lies in the principle of relevance when referring to proverbs. Even if relevance theory is not a theory of linguistic structure - and many translation problems imply structural mismatches - relevance theory offers insights about contextual information. Proverbs are seen as texts in themselves. My analysis will target the ethnofields of ‘to buy’ and ‘to sell’ in English proverbs and their Romanian corresponding versions.

  19. Probing for Relevance: Information Theories and Translation

    Daniel Dejica


    Full Text Available Recent studies claim that the more translators know about the structure and the dynamics of discourse, the more readily and accurately they can translate both the content and the spirit of a text. Similarly, international research projects highlight directions of research which aim at helping translators make reasonable and consistent decisions as to the relevance and reliability of source text features in the target text. Other recent studies stress the importance of developing information structure theories for translation. In line with such current research desiderata, the aim of this article is to test the relevance of information theories for translation. In the first part, information theories are presented from different linguistic perspectives. In the second part, their relevance for translation is tested on a series of texts by examining how they have been or can be applied to translation. The last part presents the conclusions of the analysis.

  20. Passage relevance models for genomics search

    Frieder Ophir


    Full Text Available Abstract We present a passage relevance model for integrating syntactic and semantic evidence of biomedical concepts and topics using a probabilistic graphical model. Component models of topics, concepts, terms, and document are represented as potential functions within a Markov Random Field. The probability of a passage being relevant to a biologist's information need is represented as the joint distribution across all potential functions. Relevance model feedback of top ranked passages is used to improve distributional estimates of query concepts and topics in context, and a dimensional indexing strategy is used for efficient aggregation of concept and term statistics. By integrating multiple sources of evidence including dependencies between topics, concepts, and terms, we seek to improve genomics literature passage retrieval precision. Using this model, we are able to demonstrate statistically significant improvements in retrieval precision using a large genomics literature corpus.

  1. National Geochemical Database: Concentrate

    U.S. Geological Survey, Department of the Interior — Geochemistry of concentrates from the National Geochemical Database. Primarily inorganic elemental concentrations, most samples are from the continental US and...

  2. Urine concentration test

    ... page: // Urine concentration test To use the sharing features on this page, please enable JavaScript. A urine concentration test measures the ability of the kidneys to ...

  3. Mining chemical reactions using neighborhood behavior and condensed graphs of reactions approaches.

    de Luca, Aurélie; Horvath, Dragos; Marcou, Gilles; Solov'ev, Vitaly; Varnek, Alexandre


    This work addresses the problem of similarity search and classification of chemical reactions using Neighborhood Behavior (NB) and Condensed Graphs of Reaction (CGR) approaches. The CGR formalism represents chemical reactions as a classical molecular graph with dynamic bonds, enabling descriptor calculations on this graph. Different types of the ISIDA fragment descriptors generated for CGRs in combination with two metrics--Tanimoto and Euclidean--were considered as chemical spaces, to serve for reaction dissimilarity scoring. The NB method has been used to select an optimal combination of descriptors which distinguish different types of chemical reactions in a database containing 8544 reactions of 9 classes. Relevance of NB analysis has been validated in generic (multiclass) similarity search and in clustering with Self-Organizing Maps (SOM). NB-compliant sets of descriptors were shown to display enhanced mapping propensities, allowing the construction of better Self-Organizing Maps and similarity searches (NB and classical similarity search criteria--AUC ROC--correlate at a level of 0.7). The analysis of the SOM clusters proved chemically meaningful CGR substructures representing specific reaction signatures.

  4. When is Concentration Beneficial?

    Liron-Espana, Carmen; Lopez, Rigoberto A.


    This paper separates market power and efficiency effects of concentration in a sample of 255 U.S. manufacturing industries and computes welfare changes from rises in concentration. The empirical findings reveal that in nearly two-third of the cases, consumers lose as efficiency gains are generally pocketed by the industries. From an aggregate welfare standpoint, concentration is found to be beneficial in nearly 70% of the cases, mostly for low and moderate levels of concentration being partic...

  5. Photovoltaics. III - Concentrators

    Backus, C. E.


    Photovoltaic concentration systems that redirect sunlight falling on a surface to a smaller solar-cell surface concentrating the intensity of sunlight many times are examined. It is noted that solar cells for concentrating systems must be designed for low internal resistance as well as for high sunlight intensities. Two designs of silicon cells are presented that perform well at high concentrations; these are interdigitated back-contact cells and vertical multijunction cells. Attention is given to heat tapping of reemitted light.

  6. On synthesis of relevance and rigor


    This paper presents a critique of Freek Vermeulen’s synthesis of rigor and relevance in management research, and argues (1) at the first glance, Vermeulen’s papers are very appealing; (2) but with a closer scrutiny, we can unveil the weak and shaky foundations of his argument; (3) as a consequence, his solution of ‘adding a second loop’ to make management research meet dual needs of rigor and relevance is illusory and merely an applied science fiction; (4) and finally, there ar...

  7. Improved Relevance Ranking in WebGather

    LEI Ming; WANG Jianyong; CHEN Baojue; LI Xiaoming


    The amount of information on the web is growing rapidly, and search engines that rely on keyword matching usually return too many low quality matches. To improve search results, a challenging task for search engines is how to effectively calculate a relevance ranking for each web page. This paper discusses in what order a search engine should return the URLs it has produced in response to a user's query, so as to show more relevant pages first.Emphasis is given on the ranking functions adopted by WebGather that take link structure and user popularity factors into account. Experimental results are also presented to evaluate the proposed strategy.

  8. Relevance of Search Engines for Modern Generations

    Trilok Gupta


    Full Text Available Web search engines have major impact in people‟s everyday life . It is of great i m p o r t a n c e to test the retrieval effectiveness of search e n g i n e s. However, it is labour-intensive to judge the relevance of search results for a large number of queries, and these relevance judgments may not be reusable since the Web data change all the time. Experiments on major search engines show that our approach mines many high- confidence rules that help understand search engines and detect suspicious search results.

  9. Rheology of concentrated biomass

    J.R. Samaniuk; J. Wang; T.W. Root; C.T. Scott; D.J. Klingenberg


    Economic processing of lignocellulosic biomass requires handling the biomass at high solids concentration. This creates challenges because concentrated biomass behaves as a Bingham-like material with large yield stresses. Here we employ torque rheometry to measure the rheological properties of concentrated lignocellulosic biomass (corn stover). Yield stresses obtained...

  10. Firefighter Nozzle Reaction

    Chin, Selena K.; Sunderland, Peter B.; Jomaas, Grunde


    Nozzle reaction and hose tension are analyzed using conservation of fluid momentum and assuming steady, inviscid flow and a flexible hose in frictionless contact with the ground. An expression that is independent of the bend angle is derived for the hose tension. If this tension is exceeded owing...... to anchor forces, the hose becomes straight. The nozzle reaction is found to equal the jet momentum flow rate, and it does not change when an elbow connects the hose to the nozzle. A forward force must be exerted by a firefighter or another anchor that matches the forward force that the jet would exert...... on a perpendicular wall. Three reaction expressions are derived, allowing it to be determined in terms of hose diameter, jet diameter, flow rate, and static pressure upstream of the nozzle. The nozzle reaction predictions used by the fire service are 56% to 90% of those obtained here for typical firefighting hand...

  11. Oral Hypersensitivity Reactions

    ... food, food additives, drugs, oral hygiene products, and dental materials. Q: Are there any specific foods that are ... dental treatment trigger a hypersensitivity reaction? A: Some dental materials used by the dentist can cause a hypersensitivity ...

  12. Response reactions: equilibrium coupling.

    Hoffmann, Eufrozina A; Nagypal, Istvan


    It is pointed out and illustrated in the present paper that if a homogeneous multiple equilibrium system containing k components and q species is composed of the reactants actually taken and their reactions contain only k + 1 species, then we have a unique representation with (q - k) stoichiometrically independent reactions (SIRs). We define these as coupling reactions. All the other possible combinations with k + 1 species are the coupled reactions that are in equilibrium when the (q - k) SIRs are in equilibrium. The response of the equilibrium state for perturbation is determined by the coupling and coupled equilibria. Depending on the circumstances and the actual thermodynamic data, the effect of coupled equilibria may overtake the effect of the coupling ones, leading to phenomena that are in apparent contradiction with Le Chatelier's principle.

  13. Autocatalysis in reaction networks.

    Deshpande, Abhishek; Gopalkrishnan, Manoj


    The persistence conjecture is a long-standing open problem in chemical reaction network theory. It concerns the behavior of solutions to coupled ODE systems that arise from applying mass-action kinetics to a network of chemical reactions. The idea is that if all reactions are reversible in a weak sense, then no species can go extinct. A notion that has been found useful in thinking about persistence is that of "critical siphon." We explore the combinatorics of critical siphons, with a view toward the persistence conjecture. We introduce the notions of "drainable" and "self-replicable" (or autocatalytic) siphons. We show that: Every minimal critical siphon is either drainable or self-replicable; reaction networks without drainable siphons are persistent; and nonautocatalytic weakly reversible networks are persistent. Our results clarify that the difficulties in proving the persistence conjecture are essentially due to competition between drainable and self-replicable siphons.

  14. Translated chemical reaction networks.

    Johnston, Matthew D


    Many biochemical and industrial applications involve complicated networks of simultaneously occurring chemical reactions. Under the assumption of mass action kinetics, the dynamics of these chemical reaction networks are governed by systems of polynomial ordinary differential equations. The steady states of these mass action systems have been analyzed via a variety of techniques, including stoichiometric network analysis, deficiency theory, and algebraic techniques (e.g., Gröbner bases). In this paper, we present a novel method for characterizing the steady states of mass action systems. Our method explicitly links a network's capacity to permit a particular class of steady states, called toric steady states, to topological properties of a generalized network called a translated chemical reaction network. These networks share their reaction vectors with their source network but are permitted to have different complex stoichiometries and different network topologies. We apply the results to examples drawn from the biochemical literature.

  15. Ofloxacin induced hypersensitivity reaction

    Hari Babu Ramineni


    Full Text Available Ofloxacin is a commonly used antimicrobial agent to combat various infections. The adverse profile of quinolones includes gastrointestinal symptoms, which are the most frequent, neuropsychiatric symptoms, hematologic abnormalities are less common. We report a rare case of ofloxacin induced hypersensitivity reaction in a 57 year old female patient with complaints of rashes over the axilla, upper limb and back, abdomen, thorax associated with exfoliation of skin all over the axilla associated with severe itching. Based on history and clinical examination patient was diagnosed as ofloxacin induced hypersensitivity reaction and was successfully treated with antihistamines and corticosteroids. Pharmacovigilance should be a part of patient care in order to reduce occurrence of adverse drug reaction and also encourage practitioners in reporting so as to gather more and more data regarding adverse drug reactions. [Int J Res Med Sci 2015; 3(1.000: 349-351

  16. Chemisorption And Precipitation Reactions

    The transport and bioavailability of chemical components within soils is, in part, controlled by partitioning between solids and solution. General terms used to describe these partitioning reactions include chemisorption and precipitation. Chemisorption is inclusive of the suit...

  17. Adverse reactions to sulfites

    Yang, William H.; Purchase, Emerson C.R.


    Sulfites are widely used as preservatives in the food and pharmaceutical industries. In the United States more than 250 cases of sulfite-related adverse reactions, including anaphylactic shock, asthmatic attacks, urticaria and angioedema, nausea, abdominal pain and diarrhea, seizures and death, have been reported, including 6 deaths allegedly associated with restaurant food containing sulfites. In Canada 10 sulfite-related adverse reactions have been documented, and 1 death suspected to be sulfite-related has occurred. The exact mechanism of sulfite-induced reactions is unknown. Practising physicians should be aware of the clinical manifestations of sulfite-related adverse reactions as well as which foods and pharmaceuticals contain sulfites. Cases should be reported to health officials and proper advice given to the victims to prevent further exposure to sulfites. The food industry, including beer and wine manufacturers, and the pharmaceutical industry should consider using alternative preservatives. In the interim, they should list any sulfites in their products. PMID:4052897

  18. Allergic reactions in anaesthesia

    Krøigaard, M; Garvey, L H; Menné, T;


    BACKGROUND: The aim of this retrospective survey of possible allergic reactions during anaesthesia was to investigate whether the cause suspected by anaesthetists involved corresponded with the cause found on subsequent investigation in the Danish Anaesthesia Allergy Centre (DAAC). METHODS: Case...... notes and anaesthetic charts from 111 reactions in 107 patients investigated in the DAAC were scrutinized for either suspicions of or warnings against specific substances stated to be the cause of the supposed allergic reaction. RESULTS: In 67 cases, one or more substances were suspected. In 49...... match, the right substance being suspected, but investigations showed an additional allergen or several substances, including the right substance being suspected. CONCLUSIONS: An informed guess is not a reliable way of determining the cause of a supposed allergic reaction during anaesthesia and may put...

  19. Cross section measurements of the sup 1 sup 0 sup 2 Pd(p, gamma) sup 1 sup 0 sup 3 Ag, sup 1 sup 1 sup 6 Sn(p, gamma) sup 1 sup 1 sup 7 Sb, and sup 1 sup 1 sup 2 Sn(alpha, gamma) sup 1 sup 1 sup 6 Te reactions relevant to the astrophysical rp- and gamma-processes

    Oezkan, N; Boyd, R N; Cole, A L; Famiano, M; Gueray, R T; Howard, M; Sahin, L; Zach, J J; Haan, R D; Görres, J; Wiescher, M C; Islam, M S; Rauscher, T


    Total cross section measurements for the sup 1 sup 0 sup 2 Pd(p, gamma) sup 1 sup 0 sup 3 Ag and sup 1 sup 1 sup 6 Sn(p, gamma) sup 1 sup 1 sup 7 Sb reactions have been performed in the proton energy range 2.6 to 4.25 MeV, and for the sup 1 sup 1 sup 2 Sn(alpha, gamma) sup 1 sup 1 sup 6 Te reaction over the alpha beam energy range 7.0 to 10.5 MeV. An activation technique was used in which gamma rays from decays of the reaction products were detected off-line by two hyper-pure germanium detectors in a low background environment. Where possible, reaction rates are derived and the results compared to those of calculations generated by the NON-SMOKER and the MOST statistical model codes so as to judge their applicability for describing the cross sections needed for network calculations of nucleosynthesis in explosive astrophysical environments via the gamma- and rp-processes.

  20. Oxygen evolution reaction catalysis

    Haber, Joel A.; Jin, Jian; Xiang, Chengxiang; Gregoire, John M.; Jones, Ryan J.; Guevarra, Dan W.; Shinde, Aniketa A.


    An Oxygen Evolution Reaction (OER) catalyst includes a metal oxide that includes oxygen, cerium, and one or more second metals. In some instances, the cerium is 10 to 80 molar % of the metals in the metal oxide and/or the catalyst includes two or more second metals. The OER catalyst can be included in or on an electrode. The electrode can be arranged in an oxygen evolution system such that the Oxygen Evolution Reaction occurs at the electrode.