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Sample records for revisiting substitution kinetics

  1. The kinetics of substitution reaction of oxydiacetate and ...

    Indian Academy of Sciences (India)

    ... Journals; Journal of Chemical Sciences; Volume 127; Issue 10. The kinetics of substitution reaction of oxydiacetate and thiodiacetate copper(II) complexes with 1,10-phenanthroline and 2,2'-bipyridine. Joanna Pranczk Dagmara Jacewicz Dariusz Wyrzykowski Aleksandra Tesmar Lech Chmurzyński. Volume 127 Issue 10 ...

  2. Kinetics and mechanism of the oxidation of substituted ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 115; Issue 2. Kinetics and mechanism of the oxidation of substituted benzylamines by cetyltrimethylammonium permanganate. Raghvendra Shukla Pradeep K Sharma László Kótai Kalyan K Banerji. Physical and Theoretical Volume 115 Issue 2 April 2003 pp 129-134 ...

  3. Bundling revisited: substitute products and inter-firm discounts

    OpenAIRE

    Armstrong, Mark

    2010-01-01

    This paper extends the standard model of bundling to allow products to be substitutes and for products to be supplied by separate sellers. Whether integrated or separate, firms have an incentive to introduce bundling discounts when demand for the bundle is elastic relative to demand for stand-alone products. When products are partial substitutes, this typically gives an integrated firm a greater incentive to offer a bundle discount (relative to the standard model with additive preferences), w...

  4. Superoxide chemistry revisited: synthesis of tetrachloro-substituted methylenenortricyclenes

    OpenAIRE

    Budanur, Basavaraj M; Faiz Ahmed Khan

    2014-01-01

    An unexpected reactivity of the superoxide ion leading to the synthesis of tetrachloroaryl/vinyl-substituted nortricyclenes through its dual mode of action has been reported. KO2 was found to be superior and the only reagent to perform this kind of reaction over other conventional bases. Addition of the antioxidant BHT (2,6-di-tert-butyl-4-methylphenol) improved the yields of methylenenortricyclenes. A complete deuterium incorporation was observed in the superoxide-mediated reaction in DMSO-d...

  5. Revisiting amino acid substitution matrices for identifying distantly related proteins.

    Science.gov (United States)

    Yamada, Kazunori; Tomii, Kentaro

    2014-02-01

    Although many amino acid substitution matrices have been developed, it has not been well understood which is the best for similarity searches, especially for remote homology detection. Therefore, we collected information related to existing matrices, condensed it and derived a novel matrix that can detect more remote homology than ever. Using principal component analysis with existing matrices and benchmarks, we developed a novel matrix, which we designate as MIQS. The detection performance of MIQS is validated and compared with that of existing general purpose matrices using SSEARCH with optimized gap penalties for each matrix. Results show that MIQS is able to detect more remote homology than the existing matrices on an independent dataset. In addition, the performance of our developed matrix was superior to that of CS-BLAST, which was a novel similarity search method with no amino acid matrix. We also evaluated the alignment quality of matrices and methods, which revealed that MIQS shows higher alignment sensitivity than that with the existing matrix series and CS-BLAST. Fundamentally, these results are expected to constitute good proof of the availability and/or importance of amino acid matrices in sequence analysis. Moreover, with our developed matrix, sophisticated similarity search methods such as sequence-profile and profile-profile comparison methods can be improved further. Newly developed matrices and datasets used for this study are available at http://csas.cbrc.jp/Ssearch/.

  6. Revisiting the fundamental physical chemistry in heterogeneous photocatalysis: its thermodynamics and kinetics.

    Science.gov (United States)

    Ohtani, Bunsho

    2014-02-07

    Although the history of photocatalysis research is not so long, many researchers have studied photocatalysis and a large number of papers on photocatalysis have been published. The objectives of this review paper are to revisit the fundamentals of photocatalysis, especially its thermodynamics and kinetics, which have not been reexamined in recent studies, to clarify the problems, if any, that prevent developments in the field of photocatalysis, and to present insights for future progress.

  7. Revisiting the fundamental physical chemistry in heterogeneous photocatalysis : its thermodynamics and kinetics

    OpenAIRE

    Ohtani, Bunsho

    2014-01-01

    Although the history of photocatalysis research is not so long, many researchers have studied photocatalysis and a large number of papers on photocatalysis have been published. The objectives of this review paper are to revisit the fundamentals of photocatalysis, especially its thermodynamics and kinetics, which have not been reexamined in recent studies, to clarify the problems, if any, that prevent developments in the field of photocatalysis, and to present insights for future progress.

  8. Accelerated hydrolysis of substituted cellulose for potential biofuel production: kinetic study and modeling.

    Science.gov (United States)

    Mu, Bingnan; Xu, Helan; Yang, Yiqi

    2015-11-01

    In this work, kinetics of substitution accelerated cellulose hydrolysis with multiple reaction stages was investigated to lay foundation for mechanism study and molecular design of substituting compounds. High-efficiency hydrolysis of cellulose is critical for cellulose-based bioethanol production. It is known that, substitution could substantially decrease activation energy and increase reaction rate of acidic hydrolysis of glycosidic bonds in cellulose. However, reaction kinetics and mechanism of the accelerated hydrolysis were not fully revealed. In this research, it was proved that substitution therefore accelerated hydrolysis only occurred in amorphous regions of cellulose fibers, and was a process with multiple reaction stages. With molar ratio of substitution less than 1%, the overall hydrolysis rate could be increased for around 10 times. We also quantified the relationship between the hydrolysis rate of individual reaction stage and its major influences, including molar ratio of substitution, activation energy of acidic hydrolysis, pH and temperature. Copyright © 2015 Elsevier Ltd. All rights reserved.

  9. The validity of the kinetic collection equation revisited

    Directory of Open Access Journals (Sweden)

    L. Alfonso

    2008-02-01

    Full Text Available The kinetic collection equation (KCE describes the evolution of the average droplet spectrum due to successive events of collision and coalescence. Fluctuations and non-zero correlations present in the stochastic coalescence process would imply that the size distributions may not be correctly modeled by the KCE.

    In this study we expand the known analytical studies of the coalescence equation with some numerical tools such as Monte Carlo simulations of the coalescence process. The validity time of the KCE was estimated by calculating the maximum of the ratio of the standard deviation for the largest droplet mass over all the realizations to the averaged value. A good correspondence between the analytical and the numerical approaches was found for all the kernels. The expected values from analytical solutions of the KCE, were compared with true expected values of the stochastic collection equation (SCE estimated with Gillespie's Monte Carlo algorithm and analytical solutions of the SCE, after and before the breakdown time.

    The possible implications for cloud physics are discussed, in particular the possibility of application of these results to kernels modified by turbulence and electrical processes.

  10. The Kinetic Specificity of Plyometric Training: Verbal Cues Revisited

    Directory of Open Access Journals (Sweden)

    Louder Talin

    2015-12-01

    Full Text Available Plyometric training is a popular method utilized by strength and conditioning professionals to improve aspects of functional strength. The purpose of this study was to explore the influence of extrinsic verbal cueing on the specificity of jumping movements. Thirteen participants (age: 23.4 ± 1.9 yr, body height: 170.3 ± 15.1 cm, body mass: 70.3 ± 23.8 kg, performed four types of jumps: a depth jump “as quickly as possible” (DJT, a depth jump “as high as possible” (DJH, a countermovement jump (CMJ, and a squat jump (SJ. Dependent measures, which included measurement of strength and power, were acquired using a force platform. From the results, differences in body-weight normalized peak force (BW (DJH: 4.3, DJT: 5.6, CMJ: 2.5, SJ: 2.2, time in upward propulsion (s (DJH: 0.34, DJT: 0.20, CMJ: 0.40, SJ: 0.51, and mean acceleration (m·s-2 (DJH: 26.7, DJT: 36.2, CMJ: 19.8, SJ: 17.3 were observed across all comparisons (p = 0.001 - 0.033. Differences in the body-weight normalized propulsive impulse (BW·s (DJH: 0.55, DJT: 0.52, CMJ: 0.39, SJ: 0.39 and propulsive power (kW (DJH: 13.7, DJT: 16.5, CMJ: 11.5, SJ: 12.1 were observed across all comparisons (p = 0.001 - 0.050 except between the CMJ and SJ (p = 0.128 - 0.929. The results highlight key kinetic differences influencing the specificity of plyometric movements and suggest that verbal cues may be used to emphasize the development of reactive strength (e.g. DJT or high-velocity concentric power (e.g. DJH.

  11. Kinetics and mechanism for the substitution reactions of ...

    Indian Academy of Sciences (India)

    For the substitution with thiourea, a third reaction step, the displacement of the labilized amine, ... The activation parameters for all reactions studied suggest an ..... Its acid– base chemistry was characterized by fitting the poten- tiometric data to various acid–base models. The best fit model was found to be consistent with ...

  12. The kinetics of substitution reaction of oxydiacetate and ...

    Indian Academy of Sciences (India)

    substitution reaction of Cu(II) oxydiactate and thio- diacetate complexes have also been investigated in. DMSO solution. The physico-chemical as well as acid- base properties of non-aqueous solvents including. DMSO affect coordinating properties of ligands such as pyridine derivatives and consequently it may influ-.

  13. KINETICS OF SUBSTITUTION OF CIS-BIS(MALONATO ...

    African Journals Online (AJOL)

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    The kinetics of interaction among amino acids such as glycine, DL-alanine and DL-phenylalanine ... The effect of pH, temperature and substrate was also ... formation of ion pair. The reaction between glycine and chromium(III) results in the formation of the tetra aquaglycinato chromium(III) complex [9] in the pH range of 3.0 ...

  14. Kinetics and mechanism of the ligand substitution reaction of di- ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 123; Issue 3 ... The kinetics of the interaction between diethyldithiocarbamate (Et2DTC) and the title complex has been studied spectrophotometrically in aqueous medium as a function of nucleophile concentration, temperature and pH at constant ionic strength.

  15. Lipase-Catalyzed Kinetic Resolution of Novel Antifungal N-Substituted Benzimidazole Derivatives.

    Science.gov (United States)

    Łukowska-Chojnacka, Edyta; Staniszewska, Monika; Bondaryk, Małgorzata; Maurin, Jan K; Bretner, Maria

    2016-04-01

    A series of new N-substituted benzimidazole derivatives was synthesized and their antifungal activity against Candida albicans was evaluated. The chemical step included synthesis of appropriate ketones containing benzimidazole ring, reduction of ketones to the racemic alcohols, and acetylation of alcohols to the esters. All benzimidazole derivatives were obtained with satisfactory yields and in relatively short times. All synthesized compounds exhibit significant antifungal activity against Candida albicans 900028 ATCC (% cell inhibition at 0.25 μg concentration > 98%). Additionally, racemic mixtures of alcohols were separated by lipase-catalyzed kinetic resolution. In the enzymatic step a transesterification reaction was applied and the influence of a lipase type and solvent on the enantioselectivity of the reaction was studied. The most selective enzymes were Novozyme SP 435 and lipase Amano AK from Pseudomonas fluorescens (E > 100). © 2016 Wiley Periodicals, Inc.

  16. Charge transport kinetics in a robust radical-substituted polymer/nanocarbon composite electrode

    Science.gov (United States)

    Sato, Kan; Oyaizu, Kenichi; Nishide, Hiroyuki

    We have reported a series of organic radical-substituted polymers as new-type charge storage and transport materials which could be used for energy related devices such as batteries and solar cells. Redox-active radical moieties introduced to the non-conjugated polymer backbones enable the rapid electron transfer among the adjacent radical sites, and thus large diffusive flux of electrical charge at a bulk scale. Here we present the elucidated charge transport kinetics in a radical polymer/single-walled carbon nanotube (SWNT) composite electrode. The synergetic effect of electrical conduction by a three-dimensional SWNT network and electron self-exchange reaction by radical polymers contributed to the 105-fold (per 1 g of added SWNT) boosting of electrochemical reactions and exceptionally large current density (greater than 1 A/cm2) as a rechargeable electrode. A totally organic-based secondary battery with a submicron thickness was fabricated to demonstrate the splendid electrochemical performances. Grants-in-Aid for Scientific Research (No. 24225003, 15J00888) and the Leading Graduate Program in Science and Engineering, from the Japanese Ministry of Education, Culture, Sports, Science and Technology (MEXT).

  17. Testing Biochemistry Revisited : How In Vivo Metabolism Can Be Understood from In Vitro Enzyme Kinetics

    NARCIS (Netherlands)

    van Eunen, Karen; Kiewiet, Jose A. L.; Westerhoff, Hans V.; Bakker, Barbara M.

    2012-01-01

    A decade ago, a team of biochemists including two of us, modeled yeast glycolysis and showed that one of the most studied biochemical pathways could not be quite understood in terms of the kinetic properties of the constituent enzymes as measured in cell extract. Moreover, when the same model was

  18. Testing biochemistry revisited: how in vivo metabolism can be understood from in vitro enzyme kinetics.

    NARCIS (Netherlands)

    van Eunen, K.; Kiewiet, J.A.L.; Westerhoff, H.V.; Bakker, B.M.

    2012-01-01

    A decade ago, a team of biochemists including two of us, modeled yeast glycolysis and showed that one of the most studied biochemical pathways could not be quite understood in terms of the kinetic properties of the constituent enzymes as measured in cell extract. Moreover, when the same model was

  19. Probing competitive enantioselective approach vectors operating in the Jacobsen-Katsuki epoxidation: a kinetic study of methyl-substituted styrenes.

    Science.gov (United States)

    Fristrup, Peter; Dideriksen, Brian B; Tanner, David; Norrby, Per-Ola

    2005-10-05

    This paper describes a study of reactivity and enantioselectivity for a series of methyl-substituted styrenes in the Jacobsen-Katsuki (Mn(salen)-catalyzed) epoxidation reaction. Competition experiments provided kinetic data for the reactivity of the seven possible methyl-substituted styrenes (mono-, di- and trisubstituted) relative to styrene itself, ee values were measured by chiral GC, and absolute configurations were secured by chemical correlation. Of particular interest was the switch in absolute configuration at the benzylic position of the epoxides derived from (Z)- and (E)-alpha,beta-dimethylstyrene, respectively. The results could be rationalized in terms of an approach vector with the phenyl substituent proximal to the salen. As opposed to alkyl groups, a proximal phenyl group has very little effect on the rate of the reaction. Consideration of distal vs proximal approach allows prediction of absolute stereochemistry as a function of alkene substitution pattern. Trisubstituted alkenes with one phenyl group cis to the alkene hydrogen can be identified as a favored substrate class in the title reaction, with both rate and selectivity close to the classic (Z)-beta-substituted styrene substrates.

  20. Effect of the substitutional groups on the electrochemistry, kinetic of thermal decomposition and kinetic of substitution of some uranyl Schiff base complexes

    Energy Technology Data Exchange (ETDEWEB)

    Asadi, Zahra; Nasrollahi, Rahele; Ranjkeshshorkaei, Mohammad; Firuzabadi, Fahimeh Dehghani [Shiraz Univ. (Iran, Islamic Republic of). Chemistry Dept.; Dusek, Michal; Fejfarova, Karla [ASCR, Prague (Czech Republic). Inst. of Physics

    2016-05-15

    Uranyl(VI) complexes, [UO{sub 2}(X-saloph)(solvent)], where saloph denotes N,N{sup '}-bis(salicylidene)-1,2-phenylenediamine and X = NO{sub 2}, Cl, Me, H; were synthesized and characterized by 61H NMR, IR, UV-Vis spectroscopy, thermal gravimetry (TG), cyclic voltammetry, elemental analysis (C.H.N) and X-ray crystallography. X-ray crystallography of [UO{sub 2}(4-nitro-saloph)(DMF)] revealed coordination of the uranyl by the tetradentate Schiff base ligand and one solvent molecule, resulting in seven-coordinated uranium. The complex of [UO{sub 2}(4-nitro-saloph)(DMF)] was also synthesized in nano form. Transmission electron microscopy image showed nano-particles with sizes between 30 and 35 nm. The TG method and analysis of Coats-Redfern plots revealed that the kinetics of thermal decomposition of the complexes is of the first-order in all stages. The kinetics and mechanism of the exchange reaction of the coordinated solvent with tributylphosphine was investigated by spectrophotometric method. The second-order rate constants at four temperatures and the activation parameters showed an associative mechanism for all corresponding complexes with the following trend: 4-Nitro > 4-Cl > H > 4-Me. It was concluded that the steric and electronic properties of the complexes were important for the reaction rate. For analysis of anticancer properties of uranyl Schiff base complexes, cell culture and MTT assay was carried out. These results showed a reduction of jurkat cell line concentration across the complexes.

  1. Testing biochemistry revisited: how in vivo metabolism can be understood from in vitro enzyme kinetics.

    Directory of Open Access Journals (Sweden)

    Karen van Eunen

    Full Text Available A decade ago, a team of biochemists including two of us, modeled yeast glycolysis and showed that one of the most studied biochemical pathways could not be quite understood in terms of the kinetic properties of the constituent enzymes as measured in cell extract. Moreover, when the same model was later applied to different experimental steady-state conditions, it often exhibited unrestrained metabolite accumulation.Here we resolve this issue by showing that the results of such ab initio modeling are improved substantially by (i including appropriate allosteric regulation and (ii measuring the enzyme kinetic parameters under conditions that resemble the intracellular environment. The following modifications proved crucial: (i implementation of allosteric regulation of hexokinase and pyruvate kinase, (ii implementation of V(max values measured under conditions that resembled the yeast cytosol, and (iii redetermination of the kinetic parameters of glyceraldehyde-3-phosphate dehydrogenase under physiological conditions.Model predictions and experiments were compared under five different conditions of yeast growth and starvation. When either the original model was used (which lacked important allosteric regulation, or the enzyme parameters were measured under conditions that were, as usual, optimal for high enzyme activity, fructose 1,6-bisphosphate and some other glycolytic intermediates tended to accumulate to unrealistically high concentrations. Combining all adjustments yielded an accurate correspondence between model and experiments for all five steady-state and dynamic conditions. This enhances our understanding of in vivo metabolism in terms of in vitro biochemistry.

  2. Testing Biochemistry Revisited: How In Vivo Metabolism Can Be Understood from In Vitro Enzyme Kinetics

    Science.gov (United States)

    van Eunen, Karen; Kiewiet, José A. L.; Westerhoff, Hans V.; Bakker, Barbara M.

    2012-01-01

    A decade ago, a team of biochemists including two of us, modeled yeast glycolysis and showed that one of the most studied biochemical pathways could not be quite understood in terms of the kinetic properties of the constituent enzymes as measured in cell extract. Moreover, when the same model was later applied to different experimental steady-state conditions, it often exhibited unrestrained metabolite accumulation. Here we resolve this issue by showing that the results of such ab initio modeling are improved substantially by (i) including appropriate allosteric regulation and (ii) measuring the enzyme kinetic parameters under conditions that resemble the intracellular environment. The following modifications proved crucial: (i) implementation of allosteric regulation of hexokinase and pyruvate kinase, (ii) implementation of Vmax values measured under conditions that resembled the yeast cytosol, and (iii) redetermination of the kinetic parameters of glyceraldehyde-3-phosphate dehydrogenase under physiological conditions. Model predictions and experiments were compared under five different conditions of yeast growth and starvation. When either the original model was used (which lacked important allosteric regulation), or the enzyme parameters were measured under conditions that were, as usual, optimal for high enzyme activity, fructose 1,6-bisphosphate and some other glycolytic intermediates tended to accumulate to unrealistically high concentrations. Combining all adjustments yielded an accurate correspondence between model and experiments for all five steady-state and dynamic conditions. This enhances our understanding of in vivo metabolism in terms of in vitro biochemistry. PMID:22570597

  3. New constraints on kinetic isotope effects during CO2(aq) hydration and hydroxylation: Revisiting theoretical and experimental data

    Science.gov (United States)

    Sade, Ziv; Halevy, Itay

    2017-10-01

    CO2 (de)hydration (i.e., CO2 hydration/HCO3- dehydration) and (de)hydroxylation (i.e., CO2 hydroxylation/HCO3- dehydroxylation) are key reactions in the dissolved inorganic carbon (DIC) system. Kinetic isotope effects (KIEs) during these reactions are likely to be expressed in the DIC and recorded in carbonate minerals formed during CO2 degassing or dissolution of gaseous CO2. Thus, a better understanding of KIEs during CO2 (de)hydration and (de)hydroxylation would improve interpretations of disequilibrium compositions in carbonate minerals. To date, the literature lacks direct experimental constraints on most of the oxygen KIEs associated with these reactions. In addition, theoretical estimates describe oxygen KIEs during separate individual reactions. The KIEs of the related reverse reactions were neither derived directly nor calculated from a link to the equilibrium fractionation. Consequently, KIE estimates of experimental and theoretical studies have been difficult to compare. Here we revisit experimental and theoretical data to provide new constraints on oxygen KIEs during CO2 (de)hydration and (de)hydroxylation. For this purpose, we provide a clearer definition of the KIEs and relate them both to isotopic rate constants and equilibrium fractionations. Such relations are well founded in studies of single isotope source/sink reactions, but they have not been established for reactions that involve dual isotopic sources/sinks, such as CO2 (de)hydration and (de)hydroxylation. We apply the new quantitative constraints on the KIEs to investigate fractionations during simultaneous CaCO3 precipitation and HCO3- dehydration far from equilibrium.

  4. Neutron scattering from myelin revisited: bilayer asymmetry and water-exchange kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Denninger, Andrew R. [Boston College, Chestnut Hill, MA 02467 (United States); Demé, Bruno; Cristiglio, Viviana [Institut Laue–Langevin (ILL), CS 20156, F-38042 Grenoble CEDEX 9 (France); LeDuc, Géraldine [European Synchrotron Radiation Facility (ESRF), CS 40220, F-38043 Grenoble CEDEX 9 (France); Feller, W. Bruce [NOVA Scientific Inc., Sturbridge, MA 01566 (United States); Kirschner, Daniel A., E-mail: kirschnd@bc.edu [Boston College, Chestnut Hill, MA 02467 (United States)

    2014-12-01

    The structure of internodal myelin in the rodent central and peripheral nervous systems has been determined using neutron diffraction. The kinetics of water exchange in these tissues is also described. Rapid nerve conduction in the central and peripheral nervous systems (CNS and PNS, respectively) of higher vertebrates is brought about by the ensheathment of axons with myelin, a lipid-rich, multilamellar assembly of membranes. The ability of myelin to electrically insulate depends on the regular stacking of these plasma membranes and on the presence of a number of specialized membrane-protein assemblies in the sheath, including the radial component, Schmidt–Lanterman incisures and the axo–glial junctions of the paranodal loops. The disruption of this fine-structure is the basis for many demyelinating neuropathies in the CNS and PNS. Understanding the processes that govern myelin biogenesis, maintenance and destabilization requires knowledge of myelin structure; however, the tight packing of internodal myelin and the complexity of its junctional specializations make myelin a challenging target for comprehensive structural analysis. This paper describes an examination of myelin from the CNS and PNS using neutron diffraction. This investigation revealed the dimensions of the bilayers and aqueous spaces of myelin, asymmetry between the cytoplasmic and extracellular leaflets of the membrane, and the distribution of water and exchangeable hydrogen in internodal multilamellar myelin. It also uncovered differences between CNS and PNS myelin in their water-exchange kinetics.

  5. Effect of axiallity of stress state on hydrogen cracking kinetics in metals -- Troiano revisited

    Energy Technology Data Exchange (ETDEWEB)

    Timmins, P. [IESCO, San Pedro, CA (United States)

    1996-10-01

    An experimental study based on the acoustic emission technique was carried out to examine how the axiallity of the stress state, as first postulated by Troiano, influenced the hydrogen cracking kinetics, in terms of delayed hydride cracking (DHC) propagation, using constant K specimens machined from Zr-2.5 wt% Nb pressure tube alloy, of 2 mm, 4 mm and 8 mm thickness. By changing the stress state from plane strain to plane stress at a constant applied stress intensity of 15 MPa{radical}m and a hydrogen level of 50 ppm, the DHC velocity was reduced, in keeping with Troiano`s hypothesis. An explanation of how the observations made on these specimens can be related to other hydrogen cracking mechanisms, is presented.

  6. The validity of the kinetic collection equation revisited – Part 2: Simulations for the hydrodynamic kernel

    Directory of Open Access Journals (Sweden)

    L. Alfonso

    2010-08-01

    Full Text Available The kinetic collection equation (KCE has been widely used to describe the evolution of the average droplet spectrum due to the collection process that leads to the development of precipitation in warm clouds. This deterministic, integro-differential equation only has analytic solution for very simple kernels. For more realistic kernels, the KCE needs to be integrated numerically. In this study, the validity time of the KCE for the hydrodynamic kernel is estimated by a direct comparison of Monte Carlo simulations with numerical solutions of the KCE. The simulation results show that when the largest droplet becomes separated from the smooth spectrum, the total mass calculated from the numerical solution of the KCE is not conserved and, thus, the KCE is no longer valid. This result confirms the fact that for kernels appropriate for precipitation development within warm clouds, the KCE can only be applied to the continuous portion of the mass distribution.

  7. A Study on Nucleation, Crystallization Kinetics, Microstructure and Mechanical Properties of Ru-Bi Partial Substituted BSCCO Glass Ceramics

    Science.gov (United States)

    Tasci, Ahmet Tolga; Ozturk, Ozgur; Gokcen, Tugba; Cavdar, Sukru; Koralay, Haluk; Senol, Abdulkadir

    2015-03-01

    This study deals with, the effects of Ru-Bi partial substitutions on the thermal, structural and mechanical properties of Bi1 . 8 - xRuxPb0.2Sr2CaCu2O10+δ (x =0.0, 0.025, 0.050, 0.075), produced with glass-ceramics method have been investigated. The effects of Ru-Bi Partial substitutions on glass transition, nucleation and crystallization temperature are analyzed by differential thermal analyzer (DTA). Furthermore, micro-structure and micro-mechanical properties of Ru-Bi partial substituted BSCCO glass ceramics have been investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and Vickers microhardness measurements. From the DTA results, nucleation kinetics have been obtained by using Ozawa, Augis-Bennett, Takher and Kissinger equations. Also activation energies and Avrami parameters have been found. Oxidation amount is seen to be increased with increasing Ru concentration in consequence of thermogravimetric analyses results. Moreover, Lattice parameters, volume fractions and surface morphologies of the samples are obtained from XRD and SEM measurements, respectively.

  8. The Thermodynamic and Kinetic Properties of 2-Hydroxypyridine/2-Pyridone Tautomerization: A Theoretical and Computational Revisit

    Directory of Open Access Journals (Sweden)

    Safiyah A. Hejazi

    2016-11-01

    Full Text Available The gas-phase thermal tautomerization reaction between 2-hydroxypyridine (2-HPY and 2-pyridone (2-PY was investigated by applying 6-311++G** and aug-cc-pvdz basis sets incorporated into some density functional theory (DFT and coupled cluster with singles and doubles (CCSD methods. The geometrical structures, dipole moments, HOMO-LUMO energy gaps, total hyperpolarizability, kinetics and thermodynamics functions were monitored against the effects of the corrections imposed on these functionals. The small experimental energy difference between the two tautomers of 3.23 kJ/mol; was a real test of the accuracy of the applied levels of theory. M062X and CCSD methods predicted the preference of 2-HPY over 2-PY by 5–9 kJ/mol; while B3LYP functional favoured 2-PY by 1–3 kJ/mol. The CAM-B3LYP and ωB97XD functionals yielded mixed results depending on the basis set used. The source of preference of 2-HPY is the minimal steric hindrance and electrostatic repulsion that subdued the huge hyperconjugation in 2-PY. A 1,3-proton shift intramolecular gas-phase tautomerization yielded a high average activation of 137.152 kJ/mol; while the intermolecular mixed dimer interconversion gave an average barrier height of 30.844 kJ/mol. These findings are boosted by a natural bond orbital (NBO technique. The low total hyperpolarizabilities of both tautomers mark out their poor nonlinear optical (NLO behaviour. The enhancement of the total hyperpolarizability of 2-HPY over that of 2-PY is interpreted by the bond length alternation.

  9. Kinetic reactions in thin polyaniline films revisited through Raman-impedance dynamic coupling

    Energy Technology Data Exchange (ETDEWEB)

    Wang, X.; Bernard, M.C. [CNRS, UPR 015, LISE, F-75005 Paris (France); UPMC Univ Paris 06, UPR 015, LISE, F-75005 Paris (France); Deslouis, C., E-mail: claude.deslouis@upmc.f [CNRS, UPR 015, LISE, F-75005 Paris (France); UPMC Univ Paris 06, UPR 015, LISE, F-75005 Paris (France); Joiret, S.; Rousseau, P. [CNRS, UPR 015, LISE, F-75005 Paris (France); UPMC Univ Paris 06, UPR 015, LISE, F-75005 Paris (France)

    2011-04-01

    Recently introduced as a new technique in electrochemistry, the Raman-impedance dynamic coupling allows one characterizing transfer functions so far not accessible to experiment such as instantaneous concentrations of adsorbed species in response to potential modulations. These were assessed from the measurement of the time-dependent Raman band intensities of different moieties of reduced and oxidized polyaniline. The local concentrations were assumed to be proportional to these instantaneous band intensities. This technique was used to analyze the kinetics of thin polyaniline films at high pH in the limit of electronic conductivity of the film (pH {<=} 3.7). A model was developed for the different available transfer functions such as Raman (viz. concentrations)/potential, Raman/charge or classical EIS, from a mechanism based on two electron transfer between leucoemeraldine and emeraldine salt and base and a protonation reaction between the last two ones. Among the main results, the band ascribable to leucoemeraldine was found to be proportional to the total charge in the pH and potential ranges investigated which confirms the fact that it is the only reduced species involved in the redox process. A frequency-dependent relaxation was found for emeraldine base vs. charge, with an increase in intensity and a decrease of the characteristic frequency when both the pH and potential increased. Emeraldine salt (polaronic) showed practically no relaxation vs. charge at variance with the bipolaronic one but the response of the latter remained weak and noisy. An improvement in the accuracy of the coupled techniques would bring information that could not be resolved by any of the other alternative techniques alone.

  10. Kinetic response study in chemiresistive gas sensor based on carbon nanotube surface functionalized with substituted phthalocyanines

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, Anshul Kumar; Saini, Rajan; Bedi, R. K.; Mahajan, Aman, E-mail: dramanmahajan@yahoo.co.in, E-mail: anshulsharma.phy@gmail.com [Material Science Laboratory, Department of Physics, Guru Nanak Dev University, Amritsar 143005 (India); Kumar, Pankaj [Department of Applied Sciences, I.K. Gujral Punjab Technical University, Kapurthala 144601 (India)

    2016-05-06

    A kind of hybrid material is prepared by functionalizing multi-wall carbon nanotubes (MWCNTs-COOH) with substituted copper phthalocyanine and the formation of CuPcOC{sub 8}/MWCNTs-COOH hybrid is confirmed by scanning electron microscopy and transmission electron microscopy. The results indicated that on the surface of nanotubes substituted CuPcOC{sub 8} derivatives has been successfully anchored through π-π stacking interaction. The gas sensing application of the fabricated hybrid material is tested upon exposure to different hazardous species, specifically NO{sub 2}, NO, Cl{sub 2} and NH{sub 3} at operating temperature of 150°C. It has been demonstrated that for Cl{sub 2} minimum detection limit of CuPcOC{sub 8}/MWCNTs-COOH hybrid is 100 ppb. The response of hybrid sensor is found to be increased with increase in the concentration of Cl{sub 2}.

  11. The Kinetics of Mo(Co)6 Substitution Monitored by Fourier Transform Infrared Spectrophotometry.

    Science.gov (United States)

    Suslick, Kenneth S.; And Others

    1987-01-01

    Describes a physical chemistry experiment that uses Fourier transform (FTIR) spectrometers and microcomputers as a way of introducing students to the spectral storage and manipulation techniques associated with digitized data. It can be used to illustrate FTIR spectroscopy, simple kinetics, inorganic mechanisms, and Beer's Law. (TW)

  12. Kinetics of the reaction of 5-substituted orotic acids with diazodiphenylmethane

    Directory of Open Access Journals (Sweden)

    ALEKSANDAR D. MARINKOVIC

    2004-11-01

    Full Text Available Rate konstants for the reaction of eight 5-substituted orotic acids with diazodiphenylmethane (DDM in dimethylformamide (DMF were determined at 30 ºC by the known spectrophotometric method. The determined rate constants were correlated with the equations: log k2 = as1 + bsR + h log k2 = as1 + bsR + yn + h to detect the presence and investigate the influence of both electrical and steric substituent effects. The obtained results show that the electrical effect (the localized – field and delocalized – resonance is predominant and that the steric effect, althought present, is releatively small in this reaction.

  13. Solvent effects on kinetics of an heteroatomic nucleophilic substitution reaction in ionic liquid and molecular solvents mixtures

    Science.gov (United States)

    Salari, Hadi; Pedervand, Mohsen; Sadeghzadeh-Darabi, Faramarz; Gholami, Mohammad Reza

    2013-12-01

    Rate constants, k A, for the aromatic nucleophilic substitution reaction of 2-chloro-3,5-dinitropyridine with aniline were determined in different compositions of 2-propanol mixed with hexane, benzene, and 2-methylpropan-2-ol and 1-ethyl-3-methylimidazolium ethylsulfate ([Emim][EtSO4]) with dimethyl sulfoxide at 25°C. The obtained rate constants of the reaction in pure solvents are in the following order: 2-methylpropan-2-ol > dimethyl sulfoxide > 2-propanol > hexane > benzene > [Emim][EtSO4]. Molecularmicroscopic solvent parameters corresponding to the selected binary mixtures were utilized to study the kinetics of a nucleophilic substitution reaction in order to investigate and compare the effects of the solvents on a chemical process. The influence of solvent parameters including normalized polarity ( E {/T N }), dipolarity/polarizability (π*), hydrogen bond donor acidity (α), and hydrogen bond acceptor basicity (β) on the second-order rate constants were investigated and multiple linear regressions gave much better results with regard to single parameter regressions. The dipolarity/polarizability of media has a positive effect in all mixtures regarding zwitterionic character of the reaction intermediate and the hydrogen bond acceptor basicity of the solvent by stabilizing of activated complex increases the reaction rate.

  14. NBT-PABA test to assess efficiency and kinetics of substituted proteolytic enzyme action in pancreatic duct ligated minipigs.

    Science.gov (United States)

    Mösseler, A; Bergemann, J; Becker, C; Stemme, K; Gregory, P C; Kamphues, J

    2008-06-01

    The NBT-PABA test is an established method for diagnosis of pancreatic exocrine insufficiency. In the present study the NBT-PABA test was used to test and compare the efficacy of two multienzyme preparations (product A and B) differing in galenic preparation in minipigs in which pancreatic exocrine insufficiency (PEI) was induced by pancreatic duct ligation. Without enzyme substitution no distinct increase in PABA was found in blood after oral administration of NBT-PABA. Administration of both enzyme preparations led to a clear dose dependent rise in PABA-concentrations in blood. Interestingly, the two preparations showed different time curves of serum PABA concentration, indicating differences in the kinetic of proteolytic enzyme action. It is concluded that the NBT-PABA test can be a very useful test for indirectly evaluating proteolytic enzyme efficacy in vivo, and also gives information about the kinetics of enzyme action, not only the end-result of enzyme action (like digestibility trials which were used traditionally). A single test is performed in a few hours and there is no need for fistulated animals.

  15. Stereoselectivity and substrate specificity in the kinetic resolution of methyl-substituted 1-oxaspiro[2.5]octanes by Rhodotorula glutinis epoxide hydrolase

    NARCIS (Netherlands)

    Weijers, C.A.G.M.; Meeuwse, P.; Herpers, R.L.J.M.; Franssen, M.C.R.; Sudhölter, E.J.R.

    2005-01-01

    [GRAPHICS] The kinetic resolution of a range of methyl-substituted 1-oxaspiro[2.5]octanes by yeast epoxide hydrolase (YEH) from Rhodotorula glutinis has been investigated. The structural determinants of substrate specificity and stereoselectivity of YEH toward these substrates appeared to be the

  16. Enzyme kinetics and substrate selectivities of rat glutathione S-transferase isoenzymes towards a series of new 2-substituted 1-chloro-4-nitrobenzenes

    NARCIS (Netherlands)

    Aar, E.M. van der; Buikema, D.; Commandeur, J.N.M.; Koppele, J.M. te; Ommen, B. van; Bladeren, P.J. van; Vermeulen, N.P.E.

    1996-01-01

    1. Four different rat glutathione S-transferase (GST) isoenzymes, belonging to three different classes, were examined for their GSH conjugating capacity towards 11 2-substituted 1-chloro-4-nitrobenzene derivatives. Significant differences were found in their enzyme kinetic parameters K(m), k(cat)

  17. Multiple and substitute addictions involving prescription drugs misuse among 12th graders: gateway theory revisited with Market Basket Analysis.

    Science.gov (United States)

    Jayawardene, Wasantha Parakrama; YoussefAgha, Ahmed Hassan

    2014-01-01

    This study aimed to identify the sequential patterns of drug use initiation, which included prescription drugs misuse (PDM), among 12th-grade students in Indiana. The study also tested the suitability of the data mining method Market Basket Analysis (MBA) to detect common drug use initiation sequences in large-scale surveys. Data from 2007 to 2009 Annual Surveys of Alcohol, Tobacco, and Other Drug Use by Indiana Children and Adolescents were used for this study. A close-ended, self-administered questionnaire was used to ask adolescents about the use of 21 substance categories and the age of first use. "Support%" and "confidence%" statistics of Market Basket Analysis detected multiple and substitute addictions, respectively. The lifetime prevalence of using any addictive substance was 73.3%, and it has been decreasing during past few years. Although the lifetime prevalence of PDM was 19.2%, it has been increasing. Males and whites were more likely to use drugs and engage in multiple addictions. Market Basket Analysis identified common drug use initiation sequences that involved 11 drugs. High levels of support existed for associations among alcohol, cigarettes, and marijuana, whereas associations that included prescription drugs had medium levels of support. Market Basket Analysis is useful for the detection of common substance use initiation sequences in large-scale surveys. Before initiation of prescription drugs, physicians should consider the adolescents' risk of addiction. Prevention programs should address multiple addictions, substitute addictions, common sequences in drug use initiation, sex and racial differences in PDM, and normative beliefs of parents and adolescents in relation to PDM.

  18. Equilibrium and kinetics studies on the adsorption of substituted phenols by a Cu–Al layered double hydroxide intercalated with 1-naphthol-3,8-disulfonate

    Energy Technology Data Exchange (ETDEWEB)

    Kameda, Tomohito, E-mail: kameda@env.che.tohoku.ac.jp; Uchiyama, Tomomi; Yoshioka, Toshiaki

    2016-06-15

    Cu–Al layered double hydroxides (Cu–Al LDHs) intercalated with 1-naphthol-3,8-disulfonate (1-N-3,8-DS{sup 2−}) were confirmed to easily take up substituted phenols with electron-poor benzene rings from aqueous solution. The uptake of the substituted phenols by the 1-N-3,8-DS• Cu–Al LDH was better expressed by the Langmuir-type than the Dubinin−Radushkevich (DR) adsorption model. The negative values of ΔG for all substituted phenols indicate that the adsorption process is spontaneous regardless of the temperature. The |ΔH| values for all substituted phenols are less than 20 kJ mol{sup −1}, indicating that the phenol uptake by this LDH can be considered a physical adsorption process caused by π–π stacking interactions. Although the uptake of the substituted phenols by the 1-N-3,8-DS• Cu–Al LDH can be considered a physical adsorption process caused by π–π stacking interactions, it is closely related chemically to Langmuir-type adsorption. The uptake of various substituted phenols by 1-N-3,8-DS• Cu–Al LDH followed the pseudo-second-order kinetic model. By fitting the results of phenol uptake by 1-N-3,8-DS• Cu–Al LDH to the Eyring equation, it was found that positive values of ΔH{sup ‡} and ΔG{sup ‡} indicated the presence of an energy barrier in the adsorption process. Furthermore, the positive value of ΔH{sup ‡} confirmed that the process was endothermic. - Highlights: • The uptake of the substituted phenols was better expressed by the Langmuir-type. • The uptake can be considered a physical adsorption process caused by π–π stacking interactions. • The uptake followed the pseudo-second-order kinetic model.

  19. Oxidation of aniline and some para-substituted anilines by benzimidazolium fluorochromate in aqueous acetic acid medium – A kinetic and mechanistic study

    Directory of Open Access Journals (Sweden)

    S. Sheik Mansoor

    2014-04-01

    Full Text Available The oxidation kinetics of some para-substituted anilines by benzimidazolium fluorochromate (BIFC have been studied in aqueous acetic acid media in the presence of perchloric acid. The reaction is first order with respect to both aniline and BIFC and is catalysed by a hydrogen ion. The rate data obey Hammett relationship. The products of oxidation are the corresponding azo benzenes. Based on the kinetic results and product analysis, a suitable mechanism has been proposed for the reaction of BIFC with anilines.

  20. Stereoselectivity and substrate specificity in the kinetic resolution of methyl-substituted 1-oxaspiro[2.5]octanes by Rhodotorula glutinis epoxide hydrolase.

    Science.gov (United States)

    Weijers, Carel A G M; Meeuwse, Petra; Herpers, Robert L J M; Franssen, Maurice C R; Sudhölter, Ernst J R

    2005-08-19

    The kinetic resolution of a range of methyl-substituted 1-oxaspiro[2.5]octanes by yeast epoxide hydrolase (YEH) from Rhodotorula glutinis has been investigated. The structural determinants of substrate specificity and stereoselectivity of YEH toward these substrates appeared to be the configuration of the epoxide ring and the substitution pattern of the cyclohexane ring. For all compounds tested, O-axial epoxides were hydrolyzed faster than the corresponding O-equatorial compounds. In concern of the ring substituents, YEH preferred methyl groups on the Re side of the ring. Placement of substituents close to the spiroepoxide carbon decreased the reaction rate but increased enantioselectivity. YEH-catalyzed kinetic resolutions of 4-methyl 1-oxaspiro[2.5]octane epimers were most enantioselective (E > 100).

  1. Mechanism of the Fischer reaction. Effect of electronic factors on the kinetics of the rearrangement of m-substituted cyclohexanone arylhydrazones to tetrahydrocarbazoles

    Energy Technology Data Exchange (ETDEWEB)

    Przheval' skii, N.M.; Kostromina, L.Yu.; Grandberg, I.I.

    1986-03-01

    The kinetics of the thermal and acid-catalyzed Fischer indolization of m-substituted cyclohexanone arylhydrazones were studied. It was shown that substituents with different natures (-CH/sub 3/, -Cl) and the polarity of the solvent have little effect on the rate of the rearrangement. The results obtained were interpreted within the framework of the concerted mechanism for the formation of the carbon-carbon bond ((3,3)-sigmatropic rearrangement).

  2. Thermal Thiocyanate Ligand Substitution Kinetics of the Solar Cell Dye N719 by Acetonitrile, 3-Methoxypropionitrile, and 4-tert-Butylpyridine

    DEFF Research Database (Denmark)

    Nguyen, Thai Hoang; Minh, Ha; Lund, Torben

    2007-01-01

    The kinetics of the thiocyanate substitution of the solar cell sensitizer [Ru(Hdcbpy)B2B(NCS)B2B]P2-P, 2 (n-CB4BHB9B)B4BNP+)P, (HB2Bdcbpy = L = 2,2´-bipyridine-4,4´-dicarboxylic acid), known as N719, by acetonitrile, 3-methoxypropionitrile, and 4-tert-butylpyridine (4-TBP) have been determined...

  3. Syntheses, kinetics, and mechanism of ligand substitution reactions of 17-electron cyclopentadienyl and pentadienyl vanadium carbonyl complexes

    Energy Technology Data Exchange (ETDEWEB)

    Kowaleski, R.M.; Basolo, F.; Trogler, W.C.; Gedridge, R.W.; Newbound, T.D.; Ernst, R.D.

    1987-08-05

    Reported are the syntheses of bis(eta/sup 5/-pentadienyl)vanadium carbonyls and corresponding triethylphosphine compounds. The CO substitution lability in the complexes (eta/sup 5/-L)/sub 2/ VCO (L = C/sub 5/H/sub 5/, C/sub 5/Me/sub 5/, C/sub 5/H/sub 7/, 2,4-C/sub 7/H/sub 11/) was investigated. The exchange reaction of (eta/sup 5/-C/sub 5/H/sub 5/)/sub 2/V/sup 13/CO or of (eta/sup 5/-C/sub 5/Me/sub 5/)/sub 2/V/sup 13/CO with CO is first-order in both CO and metal complex: for L = C/sub 5/Me/sub 5/, kinetic parameters in toluene are ..delta..H/sub 2//sup double dagger/ = 8.9 +/- 0.7 kcal/mol, ..delta..S/sub 2//sup double dagger/ = -21 +/- 3 cal/(mol K), and k/sub 2/ (0.0/sup 0/C) = 12.7 (+/- 0.1) M/sup -1/s/sup -1/. The rate of CO addition to the 15-electron complex CP*/sub 2/V is slower than the CO exchange rate for Cp*/sub 2/VCO: ..delta..H/sup double dagger/ = 6.3 +/- 0.1 kcal/mol, ..delta..S/sup double dagger/ = -37 +/- 4 cal/(mol K), and k (0.0/sup 0/C, toluene) = 0.424 +/- 0.005 M/sup -1/ s/sup -1/. The vanadium carbonyl complexes containing one or two pentadienyl ligands react 10/sup 3/-10/sup 4/ times slower than the bis(cyclopentadienyl) complexes, and the CO exchange rates depend only slightly on CO concentration. The electronic and steric features in these complexes, which allow for associative reactions for (eta/sup 5/-C/sub 5/H/sub 5/)/sub 2/ VCO and (eta/sup 5/-C/sub 5/Me/sub 5/)/sub 2/ VCO but prohibit this pathway for the pentadienyl complexes, are discussed.

  4. kinetics

    Directory of Open Access Journals (Sweden)

    D. E. Panayotounakos

    2002-01-01

    Full Text Available We present the construction of the general solutions concerning the one-dimensional (1D fully dynamic nonlinear partial differential equations (PDEs, for the erosion kinetics. After an uncoupling procedure of the above mentioned equations a second–order nonlinear PDE of the Monge type governing the porosity is derived, the general solution of which is constructed in the sense that a full complement of arbitrary functions (as many as the order is introduced. Afterwards, we specify the above solution according to convenient initial conditions.

  5. Water-soluble Mo3S4 clusters bearing hydroxypropyl diphosphine ligands: synthesis, crystal structure, aqueous speciation, and kinetics of substitution reactions.

    Science.gov (United States)

    Basallote, Manuel G; Fernández-Trujillo, M Jesús; Pino-Chamorro, Jose Ángel; Beltrán, Tomás F; Corao, Carolina; Llusar, Rosa; Sokolov, Maxim; Vicent, Cristian

    2012-06-18

    The [Mo(3)S(4)Cl(3)(dhprpe)(3)](+) (1(+)) cluster cation has been prepared by reaction between Mo(3)S(4)Cl(4)(PPh(3))(3) (solvent)(2) and the water-soluble 1,2-bis(bis(hydroxypropyl)phosphino)ethane (dhprpe, L) ligand. The crystal structure of [1](2)[Mo(6)Cl(14)] has been determined by X-ray diffraction methods and shows the typical incomplete cuboidal structure with a capping and three bridging sulfides. The octahedral coordination around each metal center is completed with a chlorine and two phosphorus atoms of the diphosphine ligand. Depending on the pH, the hydroxo group of the functionalized diphosphine can substitute the chloride ligands and coordinate to the cluster core to give new clusters with tridentate deprotonated dhprpe ligands of formula [Mo(3)S(4)(dhprpe-H)(3)](+) (2(+)). A detailed study based on stopped-flow, (31)P{(1)H} NMR, and electrospray ionization mass spectrometry techniques has been carried out to understand the behavior of acid-base equilibria and the kinetics of interconversion between the 1(+) and the 2(+) forms. Both conversion of 1(+) to 2(+) and its reverse process occur in a single kinetic step, so that reactions proceed at the three metal centers with statistically controlled kinetics. The values of the rate constants under different conditions are used to discuss on the mechanisms of opening and closing of the chelate rings with coordination or dissociation of chloride.

  6. The validity of the kinetic collection equation revisited – Part 3: Sol–gel transition under turbulent conditions

    Directory of Open Access Journals (Sweden)

    D. Baumgardner

    2013-01-01

    Full Text Available Warm rain in real clouds is produced by the collision and coalescence of an initial population of small droplets. The production of rain in warm cumulus clouds is still one of the open problems in cloud physics, and although several mechanisms have been proposed in the past, at present there is no complete explanation for the rapid growth of cloud droplets within the size range of diameters from 10 to 50 μm. By using a collection kernel enhanced by turbulence and a fully stochastic simulation method, the formation of a runaway droplet is modeled through the turbulent collection process. When the runaway droplet forms, the traditional calculation using the kinetic collection equation is no longer valid, since the assumption of a continuous distribution breaks down. There is in essence a phase transition in the system from a continuous distribution to a continuous distribution plus a runaway droplet. This transition can be associated to gelation (also called sol–gel transition and is proposed here as a mechanism for the formation of large droplets required to trigger warm rain development in cumulus clouds. The fully stochastic turbulent model reveals gelation and the formation of a droplet with mass comparable to the mass of the initial system. The time when the sol–gel transition occurs is estimated with a Monte Carlo method when the parameter ρ (the ratio of the standard deviation for the largest droplet mass over all the realizations to the averaged value reaches its maximum value. Moreover, we show that the non-turbulent case does not exhibit the sol–gel transition that can account for the impossibility of producing raindrop embryos in such a system. In the context of cloud physics theory, gelation can be interpreted as the formation of the "lucky droplet" that grows at a much faster rate than the rest of the population and becomes the embryo for runaway raindrops.

  7. Near-ambient X-ray photoemission spectroscopy and kinetic approach to the mechanism of carbon monoxide oxidation over lanthanum substituted cobaltites

    Energy Technology Data Exchange (ETDEWEB)

    Hueso, J. L.; Martinez-Martinez, D.; Cabalerro, Alfonso; Gonzalez-Elipe, Agustin Rodriguez; Mun, Bongjin Simon; Salmeron, Miquel

    2009-07-31

    We have studied the oxidation of carbon monoxide over a lanthanum substituted perovskite (La0.5Sr0.5CoO3-d) catalyst prepared by spray pyrolysis. Under the assumption of a first-order kinetics mechanism for CO, it has been found that the activation energy barrier of the reaction changes from 80 to 40 kJ mol-1 at a threshold temperature of ca. 320 oC. In situ XPS near-ambient pressure ( 0.2 torr) shows that the gas phase oxygen concentration over the sample decreases sharply at ca. 300 oC. These two observations suggest that the oxidation of CO undergoes a change of mechanism at temperatures higher than 300 oC.

  8. Kinetics, mechanism, and spectroscopy of the reversible binding of nitric oxide to aquated iron(II). An undergraduate text book reaction revisited.

    Science.gov (United States)

    Wanat, Alicja; Schneppensieper, Thorsten; Stochel, Grazyna; van Eldik, Rudi; Bill, Eckhard; Wieghardt, Karl

    2002-01-14

    A detailed kinetic and mechanistic analysis of the classical "brown-ring" reaction of [Fe(H(2)O)(6)](2+) with NO was performed using stopped-flow and laser flash photolysis techniques at ambient and high pressure. The kinetic parameters for the "on" and "off" reactions at 25 degrees C were found to be k(on) = 1.42 x 10(6) M(-1) s(-1), DeltaH(++)(on) = 37.1 +/- 0.5 kJ mol(-1), DeltaS(++)(on) = -3 +/- 2 J K(-1) mol(-1), DeltaV(++)(on) = +6.1 +/- 0.4 cm(3) mol(-1), and k(off) = 3240 +/- 750 s(-1), DeltaH(++)(off) = 48.4 +/- 1.4 kJ mol(-1), DeltaS(++)(off) = -15 +/- 5 J K(-1) mol(-1), DeltaV(++)(off) = +1.3 +/- 0.2 cm(3) mol(-1). These parameters suggest that both reactions follow an interchange dissociative (I(d)) ligand substitution mechanism, which correlates well with the suggested mechanism for the water exchange reaction on [Fe(H(2)O)(6)](2+). In addition, Mössbauer spectroscopy and EPR measurements were performed on the reaction product [Fe(H(2)O)(5)(NO)](2+). The Mössbauer and EPR parameters closely resemble those of the [FeNO](7) units in any of the other well-characterized nitrosyl complexes. It is concluded that its electronic structure is best described by the presence of high-spin Fe(III) antiferromagnetically coupled to NO(-) (S = 1) yielding the observed spin quartet ground state (S = (3)/(2)), i.e., [Fe(III)(H(2)O)(5)(NO(-))](2+), and not [Fe(I)(H(2)O)(5)(NO(+))](2+) as usually quoted in undergraduate text books.

  9. Kinetics and Mechanism of Metal Substitution and the Irving-Williams Series: Anion-Catalyzed Substitution of Nickel for Copper in Cu(amben) [=(N,N'-Ethylenebis(2-aminobenzaldiminato))copper(II)].

    Science.gov (United States)

    Busse, Susanne; Elias, Horst; Fischer, Jürgen; Poggemann, Markus; Wannowius, Klaus J.; Boca, Roman

    1998-08-10

    Visible spectrophotometry was used to study the kinetics of metal substitution in the system Cu(amben)/Ni(DMF)(6)(ClO(4))(2)/R(4)NX in DMF at 298 K and I = 0.2 M (Bu(4)NPF(6)) (H(2)amben = N,N'-ethylenebis(2-aminobenzaldimine); X = Br(-)(), SCN(-), Cl(-); DMF = N,N-dimethylformamide). The rate of nickel for copper substitution is markedly affected by the nature of the anion X, the order of reactivity being ClO(4)- analysis in the range 350-900 nm yields the experimental rate constants k(obsd)(1), k(obsd)(2), and k(obsd)(3). Rate constant k(obsd)(1) is nickel and chloride dependent, whereas k(obsd)(2) and k(obsd)(3) are not. For the rate of disappearance of Cu(amben), v = -d[Cu(amben)]/dt, it is found that v ~ [Cl](tot)(2) at [Ni(DMF)(6)(ClO(4))(2)](0) = constant and v ~ [Ni](tot)(3) at [nickel]:[chloride] = 1:2 ([Cl](tot) and [Ni](tot) refer to the total concentration of chloride and nickel, respectively). These dependencies suggest a second-order rate law, v = k(1)[Cu(amben)]["NiCl(2)"], for the first step, with k(1) = 64 +/- 8 M(-)(1) s(-)(1) at 298 K. In view of the ligand properties of Cu(amben) it is concluded that the species "NiCl(2)" is tetrahedral Ni(DMF)(2)Cl(2) which reacts with Cu(amben) as ligand to form a binuclear adduct in the first step. It is suggested that the observed rate effects of the anions X are linked with their ability to favor the formation of nickel species with reduced coordination number, such as four-coordinate Ni(DMF)(2)X(2). The mechanism of the overall process of nickel for copper substitution in Cu(amben) is discussed. The results of the analysis of the visible spectra of Cu(amben) and Ni(amben) and of MO calculations on the charge distribution in these complexes are reported.

  10. Theoretical Analysis on the Kinetic Isotope Effects of Bimolecular Nucleophilic Substitution (SN2 Reactions and Their Temperature Dependence

    Directory of Open Access Journals (Sweden)

    Wan-Chen Tsai

    2013-04-01

    Full Text Available Factors affecting the kinetic isotope effects (KIEs of the gas-phase SN2 reactions and their temperature dependence have been analyzed using the ion-molecule collision theory and the transition state theory (TST. The quantum-mechanical tunneling effects were also considered using the canonical variational theory with small curvature tunneling (CVT/SCT. We have benchmarked a few ab initio and density functional theory (DFT methods for their performance in predicting the deuterium KIEs against eleven experimental values. The results showed that the MP2/aug-cc-pVDZ method gave the most accurate prediction overall. The slight inverse deuterium KIEs usually observed for the gas-phase SN2 reactions at room temperature were due to the balance of the normal rotational contribution and the significant inverse vibrational contribution. Since the vibrational contribution is a sensitive function of temperature while the rotation contribution is temperature independent, the KIEs are thus also temperature dependent. For SN2 reactions with appreciable barrier heights, the tunneling effects were predicted to contribute significantly both to the rate constants and to the carbon-13, and carbon-14 KIEs, which suggested important carbon atom tunneling at and below room temperature.

  11. Site specific ligand substitution in cubane-type Mo3FeS(4)(4+) clusters: kinetics and mechanism of reaction and isolation of mixed ligand Cl/SPh complexes.

    Science.gov (United States)

    Algarra, Andrés G; Basallote, Manuel G; Fernandez-Trujillo, M J; Llusar, Rosa; Pino-Chamorro, Jose A; Sorribes, Ivan; Vicent, Cristian

    2010-04-21

    The synthesis, crystal structure and solution characterization of the cubane-type [Mo(3)(FeCl)S(4)(dmpe)(3)Cl(3)] (1) (dmpe = 1,2-bis(dimethylphophane-ethane)) cluster are reported and the ligand substitution processes of chloride by thiophenolate investigated. The kinetics and the intimate mechanism of these substitutions reveal that compound 1 undergoes a number of Fe and Mo site specific ligand substitution reactions in acetonitrile solutions. In particular, PhS(-) coordination at the tetrahedral Fe site proceeds in a single resolved kinetic step whereas such substitutions at the Mo sites proceed more slowly. The effect of the presence of acids in the reaction media is also investigated and reveals that an acid excess hinders substitution reactions both at the Fe and Mo sites; however, an acid-promoted solvolysis of the Fe-Cl bonds is observed. Electrospray ionization (ESI) and tandem (ESI-MS/MS) mass spectrometry allow the identification of all the reaction intermediates proposed on the basis of stopped-flow measurements. The distinctive site specific reactivity made it possible to isolate two new clusters of the Mo(3)FeS(4)(4+) family featuring mixed chlorine/thiophenolate ligands, namely Mo(3)S(4)(FeSPh)(dmpe)(3)Cl(3) (2) and [Mo(3)S(4)(FeSPh)(dmpe)(3)(SPh)(3)] (3). A detailed computational study has also been carried out to understand the details of the mechanism of substitution at the M-Cl (M = Mo and Fe) bonds as well as the solvolysis at the Fe-Cl sites, with particular emphasis on the role of acids on the substitution process. The results of the calculations are in agreement with the experimental observations, thus justifying the non-existence of an accelerating effect of acids on the thiophenolate substitution reaction, which differs from previous proposals for the Fe(4)S(4) and MoFe(3)S(4) clusters and some related compounds.

  12. Marking with radioactive iodine of a plasma substitute and preliminary essays of his kinetic behaviour in rats; Marcacao com radioiodo de um sucedaneo do plasma e ensaios preliminares de seu comportamento cinetico em ratos

    Energy Technology Data Exchange (ETDEWEB)

    Cova, Wilma Guimaraes

    1973-07-01

    A blood plasma substitute (Haem accel - PGO), which has as a base a degraded and polymerized gelatin, was labelled with radioactive iodine (I-131) and preliminary essays of its kinetic behavior was done. We have used the labelling method of McFarlaner. The results obtained - radiochemical yield and purity - were favorable. The kinetic behaviour the residual radioactivity studied by measuring the residual radioactivity of the body and excreta in groups of male Wistar rats for a maximum period of 150 hours. These results have shown and excellent correlation for a two components exponential function's adjustment, suggesting therefore a bi compartmental mathematical model. (author)

  13. Lys98 substitution in human AP endonuclease 1 affects the kinetic mechanism of enzyme action in base excision and nucleotide incision repair pathways.

    Directory of Open Access Journals (Sweden)

    Nadezhda A Timofeyeva

    Full Text Available Human apurinic/apyrimidinic endonuclease 1 (APE1 is a key enzyme in the base excision repair (BER and nucleotide incision repair (NIR pathways. We recently analyzed the conformational dynamics and kinetic mechanism of wild-type (wt protein, in a stopped-flow fluorescence study. In this study, we investigated the mutant enzyme APE1K98A using the same approach. Lys98 was known to hydrogen bond to the carboxyl group of Asp70, a residue implicated in binding the divalent metal ion. Our data suggested that the conformational selection and induced fit occur during the enzyme action. We expanded upon the evidence that APE1 can pre-exist in two conformations. The isomerization of an enzyme-product complex in the BER process and the additional isomerization stage of enzyme-substrate complex in the NIR process were established for APE1K98A. These stages had not been registered for the wtAPE1. We found that the K98A substitution resulted in a 12-fold reduction of catalytic constant of 5'-phosphodiester bond hydrolysis in (3-hydroxytetrahydrofuran-2-ylmethyl phosphate (F, tetrahydrofuran containing substrate, and in 200-fold reduction in 5,6-dihydrouridine (DHU containing substrate. Thus, the K98A substitution influenced NIR more than BER. We demonstrated that the K98A mutation influenced the formation of primary unspecific enzyme-substrate complex in a complicated manner, depending on the Mg(2+ concentration and pH. This mutation obstructed the induced fit of enzyme in the complex with undamaged DNA and F-containing DNA and appreciably decreased the stability of primary complex upon interaction of enzyme with DNA, containing the natural apurinic/apyrimidinic (AP site. Furthermore, it significantly delayed the activation of the less active form of enzyme during NIR and slowed down the conformational conversion of the complex of enzyme with the cleavage product of DHU-substrate. Our data revealed that APE1 uses the same active site to catalyze the cleavage

  14. In Situ Tracking Kinetic Pathways of Li+/Na+Substitution during Ion-Exchange Synthesis of LixNa1.5-xVOPO4F0.5.

    Science.gov (United States)

    Park, Young-Uk; Bai, Jianming; Wang, Liping; Yoon, Gabin; Zhang, Wei; Kim, Hyungsub; Lee, Seongsu; Kim, Sung-Wook; Looney, J Patrick; Kang, Kisuk; Wang, Feng

    2017-09-13

    Ion exchange is a ubiquitous phenomenon central to wide industrial applications, ranging from traditional (bio)chemical separation to the emerging chimie douce synthesis of materials with metastable structure for batteries and other energy applications. The exchange process is complex, involving substitution and transport of different ions under non-equilibrium conditions, and thus difficult to probe, leaving a gap in mechanistic understanding of kinetic exchange pathways toward final products. Herein, we report in situ tracking kinetic pathways of Li + /Na + substitution during solvothermal ion-exchange synthesis of Li x Na 1.5-x VOPO 4 F 0.5 (0 ≤ x ≤ 1.5), a promising multi-Li polyanionic cathode for batteries. The real-time observation, corroborated by first-principles calculations, reveals a selective replacement of Na + by Li + , leading to peculiar Na + /Li + /vacancy orderings in the intermediates. Contradicting the traditional belief of facile topotactic substitution via solid solution reaction, an abrupt two-phase transformation occurs and predominantly governs the kinetics of ion exchange and transport in the 1D polyanionic framework, consequently leading to significant difference of Li stoichiometry and electrochemical properties in the exchanged products. The findings may help to pave the way for rational design of ion exchange synthesis for making new materials.

  15. Fullerenes Revisited

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 20; Issue 2. Fullerenes Revisited: Materials Chemistry and Applications of C60 Molecules. Pradeep P Shanbogh Nalini G Sundaram. General Article Volume 20 Issue 2 February 2015 pp 123-135 ...

  16. Sensemaking Revisited

    DEFF Research Database (Denmark)

    Holt, Robin; Cornelissen, Joep

    2014-01-01

    We critique and extend theory on organizational sensemaking around three themes. First, we investigate sense arising non-productively and so beyond any instrumental relationship with things; second, we consider how sense is experienced through mood as well as our cognitive skills of manipulation...... research by revisiting Weick’s seminal reading of Norman Maclean’s book surrounding the tragic events of a 1949 forest fire at Mann Gulch, USA....

  17. Superior effect of Ni-substitution on the hydrogenation kinetics of Mg{sub 6}Pd{sub 1−x}TM{sub x} (TM = Ag, Cu, Ni) pseudo-binary compounds

    Energy Technology Data Exchange (ETDEWEB)

    Ponthieu, M. [MIRE-Group, Laboratorio de Física de Materiales de Interés Energético, Dpto Física de Materiales, Facultad de Ciencias, Universidad Autónoma de Madrid, 28049 Madrid (Spain); ICMPE/CNRS-UPEC, UMR 7182, 2-8 rue Henri Dunant, 94320 Thiais (France); Fernández, J.F., E-mail: josefrancisco.fernandez@uam.es [MIRE-Group, Laboratorio de Física de Materiales de Interés Energético, Dpto Física de Materiales, Facultad de Ciencias, Universidad Autónoma de Madrid, 28049 Madrid (Spain); Cuevas, F. [ICMPE/CNRS-UPEC, UMR 7182, 2-8 rue Henri Dunant, 94320 Thiais (France); Laversenne, L. [Institut Néel, CNRS, Grenoble (France); Bodega, J.; Ares, J.R.; Sánchez, C. [MIRE-Group, Laboratorio de Física de Materiales de Interés Energético, Dpto Física de Materiales, Facultad de Ciencias, Universidad Autónoma de Madrid, 28049 Madrid (Spain)

    2015-10-05

    Highlights: • Kinetics of (de)hydrogenation of Mg{sub 6}(Pd,TM) TM = Ag, Cu and Ni compared. • Faster hydrogenation kinetics for the Ni compound. • Faster H-desorption for the Ni compound due to MgH{sub 2}/Mg{sub 2}NiH{sub 4} synergy. - Abstract: In this investigation, the H-sorption kinetics of Mg{sub 6}Pd and Mg{sub 6}Pd{sub 1−x}TM{sub x} (TM = Ag, Cu, Ni) pseudo-binary compounds at the TM solubility limit have been studied by isothermal hydrogen absorption, thermal desorption spectroscopy and in situ neutron diffraction. Among all studied compounds, the fastest absorption kinetics takes place for the Ni-substituted one. The fit of the absorption curves to established model equations for solid–gas reaction shows that hydrogenation is controlled by diffusion. As for desorption, the peak temperature for the Ni-substituted compound is 90 K below that of MgH{sub 2}/Mg system and is characterised by a low activation energy of 68 kJ/molH{sub 2}. To better understand these results, neutron diffraction experiments during in situ thermal desorption of deuterated Mg{sub 6}Pd and Mg{sub 6}Pd{sub 0.25}Ni{sub 0.75} compounds were carried out. These experiments demonstrate a synergetic effect between MgH{sub 2} and Mg{sub 2}NiH{sub 4} hydrides as responsible for the remarkable kinetics of the Ni-containing compound.

  18. Flow-Induced New Channels of Energy Exchange in Multi-Scale Plasma Dynamics – Revisiting Perturbative Hybrid Kinetic-MHD Theory

    Science.gov (United States)

    Shiraishi, Junya; Miyato, Naoaki; Matsunaga, Go

    2016-01-01

    It is found that new channels of energy exchange between macro- and microscopic dynamics exist in plasmas. They are induced by macroscopic plasma flow. This finding is based on the kinetic-magnetohydrodynamic (MHD) theory, which analyses interaction between macroscopic (MHD-scale) motion and microscopic (particle-scale) dynamics. The kinetic-MHD theory is extended to include effects of macroscopic plasma flow self-consistently. The extension is realised by generalising an energy exchange term due to wave-particle resonance, denoted by δ WK. The first extension is generalisation of the particle’s Lagrangian, and the second one stems from modification to the particle distribution function due to flow. These extensions lead to a generalised expression of δ WK, which affects the MHD stability of plasmas. PMID:27160346

  19. Flow-Induced New Channels of Energy Exchange in Multi-Scale Plasma Dynamics - Revisiting Perturbative Hybrid Kinetic-MHD Theory.

    Science.gov (United States)

    Shiraishi, Junya; Miyato, Naoaki; Matsunaga, Go

    2016-05-10

    It is found that new channels of energy exchange between macro- and microscopic dynamics exist in plasmas. They are induced by macroscopic plasma flow. This finding is based on the kinetic-magnetohydrodynamic (MHD) theory, which analyses interaction between macroscopic (MHD-scale) motion and microscopic (particle-scale) dynamics. The kinetic-MHD theory is extended to include effects of macroscopic plasma flow self-consistently. The extension is realised by generalising an energy exchange term due to wave-particle resonance, denoted by δ WK. The first extension is generalisation of the particle's Lagrangian, and the second one stems from modification to the particle distribution function due to flow. These extensions lead to a generalised expression of δ WK, which affects the MHD stability of plasmas.

  20. Revisiting the Kinetics and Thermodynamics of the Low-Temperature Oxidation Pathways of Alkanes: A Case Study of the Three Pentane Isomers

    KAUST Repository

    Bugler, John

    2015-07-16

    © 2015 American Chemical Society. This paper describes our developing understanding of low-temperature oxidation kinetics. We have investigated the ignition of the three pentane isomers in a rapid compression machine over a wide range of temperatures and pressures, including conditions of negative temperature coefficient behavior. The pentane isomers are small alkanes, yet have structures that are complex enough to allow for the application of their kinetic and thermochemical rules to larger molecules. Updates to the thermochemistry of the species important in the low-temperature oxidation of hydrocarbons have been made based on a thorough literature review. An evaluation of recent quantum-chemically derived rate coefficients from the literature pertinent to important low-temperature oxidation reaction classes has been performed, and new rate rules are recommended for these classes. Several reaction classes have also been included to determine their importance with regard to simulation results, and we have found that they should be included when developing future chemical kinetic mechanisms. A comparison of the model simulations with pressure-time histories from experiments in a rapid compression machine shows very good agreement for both ignition delay time and pressure rise for both the first- and second-stage ignition events. We show that revisions to both the thermochemistry and the kinetics are required in order to replicate experiments well. A broader validation of the models with ignition delay times from shock tubes and a rapid compression machine is presented in an accompanying paper. The results of this study enhance our understanding of the combustion of straight- and branched-chained alkanes.

  1. Living Polymerization of N -Substituted β-Alanine N -Carboxyanhydrides: Kinetic Investigations and Preparation of an Amphiphilic Block Copoly-β-Peptoid

    KAUST Repository

    Grossmann, Arlett

    2012-07-03

    Poly(α-peptoid)s (N-substituted polyglycines) are interesting peptidomimetic biomaterials that have been discussed for many applications. Poly(β-peptoid)s (N-substituted poly-β-alanines), although equally intriguing, have received much less attention. Here we present results that suggest that while N-substituted β-alanine N-carboxyanhydrides can undergo a living nucleophilic ring-opening polymerization, the solubility of poly(β-peptoid)s can be very poor, which contributes to the limited accessibility using other synthetic approaches. The living character of the polymerization was utilized for the preparation of the first polymerized amphiphilic block copoly-β-peptoid. Our results may open a new route towards highly defined functional poly(β-peptoid)s which could represent biomaterials. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Substituent and structural effects on the kinetics of the reaction of N-(substituted phenylmethylene-m- and -p-aminobenzoic acids with diazodiphenylmethane

    Directory of Open Access Journals (Sweden)

    BRATISLAV Z. JOVANOVIC

    2007-12-01

    Full Text Available The rate constants for the reaction of twenty-two N-(substituted phenyl methylene-m- and -p-aminobenzoic acids with diazodiphenylmethane were determined in absolute ethanol at 30 °C. The effects of substituents on the reactivity of the investigated compounds were interpreted by correlation of the rate constants with LFER equations. The results of quantum mechanical calculations of the mole cular structure together with experimental results gave a better insight into the effects of structure on the transmission of electronic effects of the substituents. New σ constants for substituted benzylideneamino group were calculated.

  3. The effects of substituent position on kinetics of benzene vapour adsorption onto 3-phenylphenoxy substituted metal-free and metallo-phthalocyanines thin films.

    Science.gov (United States)

    Alamin Ali, Haytham Elzien; Can, Nursel; Altun, Selçuk; Odabaş, Zafer

    2016-11-14

    The preparation of metal-free, Zn(ii), In(iii), and Cu(ii)-phthalocyanines containing tetrakis-(3-phenylphenoxy) groups was achieved by employing 3-(3-phenylphenoxy)phthalonitrile (1) and 4-(3-phenylphenoxy)phthalonitrile (2) as starting materials. The phthalonitriles and phthalocyanines were characterized by elemental analysis, infrared, proton nuclear magnetic resonance, ultraviolet-visible, and matrix-assisted laser desorption/ionization time-of-flight mass spectroscopic techniques. The effect of the substituent group on the kinetics of benzene vapour adsorption onto these novel compounds was examined using three kinetics models: the pseudo first-order model, the Elovich equation, and a simple adsorption-desorption model. Results show that the benzene adsorption kinetics strongly depend on the position of the substituent groups.

  4. Effect of chalcogen substitution in mixed Mo{sub 6}S{sub 8-n}Se{sub n} (n = 0, 1, 2) Chevrel phases on the thermodynamics and kinetics of reversible Mg ions insertion

    Energy Technology Data Exchange (ETDEWEB)

    Suresh, G.S. [Department of Chemistry, Bar-Ilan University, Ramat-Gan 52900 (Israel); Levi, M.D. [Department of Chemistry, Bar-Ilan University, Ramat-Gan 52900 (Israel)], E-mail: levimi@mail.biu.ac.il; Aurbach, D. [Department of Chemistry, Bar-Ilan University, Ramat-Gan 52900 (Israel)

    2008-04-20

    The effect of the partial substitution of S by Se atoms in the Mo{sub 6}Se{sub 8-n}S{sub n} Chevrel phases (CPs), (n = 0, 1, 2), on the reversible intercalation of Mg ions into these hosts was studied by a combination of cyclic voltammetry (CV), galvanostatic cycling, potentiostatic intermittent titration (PITT) and electrochemical impedance spectroscopy (EIS) techniques. Based on the previously published structural characterizations of the CP compounds under study, we describe herein the thermodynamic effect of the substitution in terms of the transformation of a single peak of the differential capacitance for the pure Mo{sub 6}X{sub 8} phases (X = S or Se), into a set of a lower amplitude and broader peaks for the mixed (S, Se) CPs, located at less positive potentials compared to that for the pure CP. This is due to the preferential ordering of the Se anions (as compared to that of S anions) in their sites in the CP's crystal structure. In addition to the thermodynamic effect of the substitution, the geometry of the transition state for the mobile Mg ions is modified, thus facilitating the insertion of Mg ions into the partially substituted CP compounds (the kinetic effect). Thereby, the partial charge trapping that characterizes Mg ion insertion into sulfide-based CPs at low temperatures vanishes in the Mg{sub x}Mo{sub 6}S{sub 6}Se{sub 2} compounds. This was nicely confirmed by impedance (EIS) measurements in combination with chronopotentiometry.

  5. Effect of valine 106 on structure-function relation of cytosolic human thymidine kinase - Kinetic properties and oligomerization pattern of nine substitution mutants of V106

    DEFF Research Database (Denmark)

    Frederiksen, Hanne; Berenstein, Dvora; Munch-Petersen, Birgitte

    2004-01-01

    and characterized nine mutants of amino acid 106 differing in size, conformation and polarity. According to their oligomerization pattern and thymidine kinetics, the TK1 mutants can be divided into two groups. Group I (V106A, V106I and V106T) behaves like V106WT, in that pre-assay exposure to ATP induces reversible...

  6. The stability and degradation kinetics of acetylsalicylic acid in different organic solutions revisited – an UHPLC–ESI-QTOF spectrometry study

    Directory of Open Access Journals (Sweden)

    Skibinski Robert

    2016-04-01

    Full Text Available Ultra high performance liquid chromatography (UHPLC, coupled with accurate quadrupole-time-of-flight (Q-TOF mass spectrometry, was used for the stability study of acetylsalicylic acid within a variety of different organic solutions: methanol, ethanol, propan-2-ol, acetonitrile, tetrahydrofuran and 1,4-dioxane. With the use of gradient elution chromatography and mass spectrometry detection in negative ionization, MS and MS/MS spectra were recorded simultaneously. In addition, quantitative, as well as qualitative analysis was performed during one assay. The stability of acetylsalicylic acid in such solutions was tested at room temperature, in a 12h period. In the work, in all cases, only one main degradation product, salicylic acid, was found. What is more, the work revealed that the degradation of aspirin in the tested organic solutions yields apparent second-order kinetics. The study also demonstrated that acetonitrile and 1,4-dioxane turned out to be the most stable solvents, and an above 80% of initial concentration of acetylsalicylic acid was found in this case. Furthermore, the most popular analytical solvents, methanol and ethanol, were found to be very unstable media. Herein, below 40% of initial concentration of acetylsalicylic acid was seen after 12h. The obtained results were also compared with the degradation of acetylsalicylic acid in a water solution. In this situation, only about 25% of the analyzed compound was resolved to salicylic acid in the same time frame.

  7. Kinetic and mechanistic investigation of the substitution reactions of four and five co-ordinated rhodium stibine complexes with a bulky phosphite.

    Science.gov (United States)

    Hennion, Clare; Jonasson, Klara J; Wendt, Ola F; Roodt, Andreas

    2013-10-21

    The substitution reaction of trans-[Rh(Cl)(CO)(SbPh3)2] (1) with tris(2,4-di-tert-butylphenyl)phosphite (2,4-TBPP) to form trans-[Rh(Cl)(CO)(2,4-TBPP)2] (4) in two consecutive steps has been investigated by UV-vis stopped-flow spectrophotometry. The experiments were performed in dichloromethane and in ethyl acetate, at 298 K and 268 K respectively for the first reaction step, and for the second reaction step over a temperature range from 278 to 313 K in both solvents. The first step is very fast (up to 1630 s(−1)) and on the limit of what is observable with the stopped-flow technique. Introduction of the five-coordinate complex trans-[Rh(Cl)(CO)(SbPh3)3] (2) in equilibrium with (1), by adding an excess SbPh3, led to a significant decrease in overall reaction rate for the formation of the intermediate trans-[Rh(Cl)(CO)(SbPh3)2(2,4-TBPP)] (3). Activation parameters for the second substitution reaction, in which 3 is converted to 4, has been determined as ΔH‡ = 22.85 ± 0.17 and 28.38 ± 0.10 kJ mol(−1) and ΔS‡ = −144.7 ± 0.6 and −100.9 ± 0.4 J mol(−1) K(−1) for CH2Cl2 and EtOAc respectively, supporting an associative pathway. A strongly coordinating solvent promotes both reactions. In all reaction steps a strong tendency for stibines to promote 5-coordinated, fairly stable intermediates is manifested.

  8. Influence of the aromatic substitutes in the thermal and kinetic behavior of mesoionic compounds of the 1,3-thiazole-5-tiolate system

    Energy Technology Data Exchange (ETDEWEB)

    Alves de Morais, Soraya, E-mail: sorayaamorais@yahoo.com.b [Universidade Estadual da Paraiba, Departamento de Quimica, Av. Baraunas, s/n, Campina Grande, PB (Brazil); Rogrigues da Silva Morais, Crislene, E-mail: crislene@pq.cnpq.b [Universidade Federal de Campina Grande, Unidade Academica de Engenharia de Materiais, Av. Aprigio Veloso, 882, Campina Grande, PB (Brazil); Filgueiras de Athayde Filho, Petronio, E-mail: athayde-filho@pq.cnpq.b [Universidade Federal da Paraiba, Departamento de Quimica - CCEN, 58.081-970, Joao Pessoa, PB (Brazil); Freitas Lira, Bruno, E-mail: brunofrlira@hotmail.co [Universidade Federal da Paraiba, Departamento de Quimica - CCEN, 58.081-970, Joao Pessoa, PB (Brazil); Feitosa de Souza, Marcos Antonio, E-mail: ramcos31@yahoo.com.b [Universidade Federal da Paraiba, Departamento de Quimica - CCEN, 58.081-970, Joao Pessoa, PB (Brazil)

    2010-04-16

    In this work, three mesoionic compounds of the 1,3-thiazole-5-tiolat system were studied, derived from amino acids of the glycerin through 1,3-dipolar cyclo-addition/reversion reaction. The mesoionic compounds were characterized as: MI-1 (mesoionic 2-(4-chlorophenyl)-3-methyl-4-phenyl-1,3-thiazole-5-tiolat); MI-2 (mesoionic 2-(4-chlorophenyl)-3-methyl-4-(4-isopropylphenyl)-1,3-thiazole-5-tiolat) and MI-3 (Mesoionic 2-(4-clorophenyl)-3-methyl-4-(methoxyphenyl)-1,3-thiazole-5-tiolate). These compounds were characterized by infrared spectroscopy (IR), nuclear magnetic resonance (NMR), thermogravimetry (TG) and differential scanning calorimeter (DSC). Also, the kinetic study of the thermal decomposition by non-isothermal thermogravimetry has been realized, presenting, the kinetic and thermal behavior of these compounds. The results of the spectroscopic analysis confirmed the structure of the synthesized mesoionic compounds. The DSC curves of the mesoionic compounds MI-1, MI-2, and MI-3 indicated the fusion of two of them followed by a subsequent decomposition. The TG/DTG curves showed that the decomposition of the mesoionic compounds MI-1, MI-2 and MI-3 occurred in several steps.

  9. A kinetics and mechanistic study on the role of the structural rigidity of the linker on the substitution reactions of chelated dinuclear Pt(II) complexes.

    Science.gov (United States)

    Mambanda, Allen; Jaganyi, Deogratius

    2012-01-21

    Substitution reactions of platinum complexes bearing cyclohexylamine/diamine moieties viz., [Pt(H(2)O)(N,N-bis(2-pyridylmethyl)cyclohexylamine)](CF(3)SO(3))(2), bpcHna; [{Pt(H(2)O)}(2)(N,N,N',N'-tetrakis(2-pyridylmethyl)-trans-1,4-cyclohexyldiamine)](CF(3)SO(3))(4), cHn and [{Pt(H(2)O)}(2)(N,N,N',N'-tetrakis(2-pyridylmethyl)-4,4'-dicyclohexylmethanediamine)](CF(3)SO(3))(4), dcHnm and phenylamine/diamine moieties viz., ([Pt(H(2)O)N,N-bis(2-pyridylmethyl)phenylamine)](CF(3)SO(3))(2), bpPha; [{Pt(H(2)O)}(2)(N,N,N',N'-tetrakis(2-pyridylmethyl)-1,3-phenyldiamine)](CF(3)SO(3))(4), mPh; [{Pt(H(2)O)}(2)(N,N,N',N'-tetrakis(2-pyridylmethyl)-1,4-phenyldiamine)](CF(3)SO(3))(4), pPh and [{Pt(H(2)O)}(2)(N,N,N',N'-tetrakis(2-pyridylmethyl)-4,4'-diphenylmethanediamine)](CF(3)SO(3))(4)), dPhm with thiourea nucleophiles were studied in acidified 0.01 M LiCF(3)SO(3) aqueous medium under pseudo-first-order conditions using stopped-flow and UV-visible spectrophotometric techniques. The rate of substitution follows a similar trend in the two sets of complexes and decreases in the order: bpcHna > dcHnm > cHn and bpPha > dPhm ≈ pPh ≈ mPh), respectively. The result of this study has shown that the rigidity and/or the planarity of a diamine bridge linking the two (2-pyridylmethyl)amine-chelated Pt(II) centres, influences the reactivity of the metal centres by protracting similar symmetry elements within the complexes, which determines the amount of steric influences felt on the coordination square-plane. Hence, the order of reactivity is controlled by both the steric hindrance and the magnitude of the trans σ-inductive effect originating from the linker towards the metal centre. These two factors also impact on the acidity of the complexes. The high negative entropies and low positive enthalpies support an associative mode of activation.

  10. Thiocyanate ligand substitution kinetics of the solar cell dye Z-907 by 3-methoxypropionitrile and 4-tert-butylpyridine at elevated temperatures

    DEFF Research Database (Denmark)

    Phuong, Nguyen Tuyet; Degn, Rikke; Nguyen, Thai Hoang

    2009-01-01

    The dye sensitized solar cell dye Z-907, [RuLL´(NCS)2] may loose a thiocyanate ligand at elevated temperatures (80-100 ºC) by ligand exchange with the solar cell additive 4-tert-butylpyridine (4-TBP) or the electrolyte solvent 3-methoxypropionitrile (3-MPN). The mechanism in homogeneous solution...... by HPLC coupled to UV/Vis and electrospray mass spectrometry. A half life time t1/2 = 150 h was obtained for the Z-907 dye bound to TiO2 nano crystalline particles at 85 ºC in presence of 4-TBP and 3-MPN. Dye sensitized solar cells (DSC) with Z-907 as sensitizer and application of the so called “non...... robust” electrolytes containing 4-TBP and 3-MPN is therefore not expected to be able to pass a 1000 h thermal stress test at 85 ºC. Addition of thiocyanate to the cell electrolyte may however, eliminate or reduce the problems caused by dye thiocyanate ligand substitution in DSC cells....

  11. Leukemia revisited

    Energy Technology Data Exchange (ETDEWEB)

    Cronkite, E P

    1980-01-01

    Selected features of the historical development of our knowledge of leukemia are discussed. The use of different methodologies for study of the nature of leukemic cell proliferation are analyzed. The differences between older cell kinetic data using tritiated thymidine and autoradiography and the newer cell culture methods are more apparent than real. It is suggested that tritiated thymidine and extracorporeal irradiation of the blood may be useful for therapeutic agents that have not been given an adequate trial. Radiation leukemogenesis presents an opportunity for study of the nature of leukemogenesis that has not been exploited adequately.

  12. Substitutional analysis

    CERN Document Server

    Rutherford, Daniel Edwin

    2013-01-01

    Classic monograph, suitable for advanced undergraduates and graduate students. Topics include calculus of permutations and tableaux, semi-normal representation, orthogonal and natural representations, group characters, and substitutional equations. 1968 edition.

  13. Effect of Asparagine Substitutions in the YXN Loop of a Class C β-Lactamase of Acinetobacter baumannii on Substrate and Inhibitor Kinetics

    Science.gov (United States)

    Li, Mei; Taracila, Magda A.

    2014-01-01

    Class C cephalosporinases are a growing threat, and inhibitors of these enzymes are currently unavailable. Studies exploring the YXN loop asparagine in the Escherichia coli AmpC, P99, and CMY-2 enzymes have suggested that interactions between C6′ or C7′ substituents on penicillins or cephalosporins and this Asn are important in determining substrate specificity and enzymatic stability. We sought to characterize the YXN loop asparagine in the clinically important ADC-7 class C β-lactamase of Acinetobacter baumannii. Mutagenesis at the N148 position in ADC-7 yields functional mutants (N152G, -S, -T, -Q, -A, and -C) that retain cephalosporinase activity. Using standard assays, we show that N148G, -S, and -T variants possess good catalytic activity toward cefoxitin and ceftaroline but that cefepime is a poor substrate. Because N152 variants of CMY-2, another class C β-lactamase, are more readily inhibited by tazobactam due to higher rates of inactivation, we also tested if the N148 substitutions in ADC-7 would affect inactivation by sulfone inhibitors, sulbactam and tazobactam, class A β-lactamase, and A. baumannii penicillin-binding protein (PBP) inhibitors with in vitro activity against ADC-7. The 50% inhibitory concentrations (IC50s) for tazobactam and sulbactam were improved, with 7-fold and 2-fold reductions, respectively, for the N148S variant. A homology model of the N148S ADC-7 enzyme in a Michaelis-Menten complex with tazobactam showed a loss of interaction between N148 and the sulfone moiety of the inhibitor. We postulate that this may result in more-rapid secondary ring opening of the inhibitor, as the unbound sulfone is an excellent leaving group, leading to more-rapid formation of the stable linearized inhibitor. PMID:25534745

  14. Compaction properties, drug release kinetics and fronts movement studies of matrices combining mixtures of swellable and inert polymers. III: effect of polymer substitution type.

    Science.gov (United States)

    Escudero, J J; Ferrero, C; Casas, M; Jiménez-Castellanos, M R

    2012-09-15

    Theophylline radial release from cellulose derivatives with different substitution type (HPMC K4M, HPC H, MC A4M) matrix tablets has been modulated by the introduction of a new inert polymeric excipient, at different proportions (75, 50, 25%). The new polymer was hydroxypropylcellulose-methyl methacrylate (HCMMA), which was dried either in a vacuum oven (OD-HCMMA) or freeze-dried (FD-HCMMA). MC A4M and its mixtures presented the best compaction properties results, especially mixed with FD-HCMMA, according to 100% mixtures. Only high levels of HCMMA (75%) in the matrices showed interesting differences to drug release modulation. Also, at this proportion (75:25), the HPC H mixtures presented the highest differences in relation with OD or FD HCMMA respect to the other cellulose polymers. HPMC K4M and HPC H mixtures showed a combination of diffusion and erosion release mechanisms. The last one was nearly negligible in MC A4M mixtures, according with its highest diffusion rate constant values, and the absence of hydroxypropyl substituents. Only HPMC K4M mixtures presented a diffusion front that moves outwards, while HPC H and MC A4M moves inwards. The modulation of theophylline radial release was obtained using a high percentage of HCMMA, and the use of two cellulosic ethers, one of them with just one type of substituent (MC A4M or HPC H) and the other with two types of substituent (HPMC K4M). Another possibility is changing the HCMMA copolymer (OD or FD) in the 75/25 mixture with HPC. Copyright © 2012 Elsevier B.V. All rights reserved.

  15. Biaspectuals Revisited

    Directory of Open Access Journals (Sweden)

    Zdeněk Starý

    2017-11-01

    Full Text Available The article deals with (or rather begins with Czech biaspectual verbs. Although biaspectuals (sometimes referred to as aspectual homonyms distinguish between perfective vs. imperfective meaning, there is nothing in their morphological makeup to signal this meaning distinction. To determine the aspect of a biaspectual, i.e. to disambiguate its aspectual homonymy, biaspectuals are sometimes synonymously substituted by verbs whose morphological makeup does signal their aspect; the biaspectuals are then considered perfective or imperfective (used perfectively vs. imperfectively depending on the aspect of their substituents. The article demonstrates that this method is deficient: it is not necessarily conclusive. To demonstrate this, the following observations were made and conclusions drawn on Czech aspect and aspect in general. i. Despite the fact that aspect is thought of as an obligatory verbal category in Czech, it is not a matter of the verb alone, but rather of a larger linguistic expression. The mutual morphological makeup of the verb is only one of the many factors/exponents which (“in cooperation” determine the aspectual interpretation of the respective linguistic expression. Some of these factors are identifiable as aspectual exponents in the expression itself (for example tense, verb complements, adverbial verb complements among them, others are beyond its scope, i.e. they are part of the (situational context in which the expression is used. ii. Linguistic expression can be interpreted as perfective, imperfective, aspectually unspecific or the aspectual distinction can be irrelevant for it — despite that, aspect is considered to be an obligatory category. iii. Furthermore, the morphological imperfective can be used to co-express perfectivity, and the morphological perfective can be used to refer to an imperfectively conceived process/event. Therefore, due to this and points i. and ii. above, the verb IS NOT inherently perfective

  16. Ferric ion-specific sequestering agents. 7. Synthesis, iron-exchange kinetics, and stability constants of N-substituted, sulfonated catechoylamide analogs of enterobactin

    Energy Technology Data Exchange (ETDEWEB)

    Pecoraro, Vincent L. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States); Weit, Frederick L. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States); Raymond, Kenneth N. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)

    1981-08-01

    For treatment of chronic iron overload (as occurs in Cooley's anemia), ferric ion sequestering agents with specific properties are necessary. Two analogues of enterobactin [a microbial chelating agent with the greatest stability constant known for an Fe(III) complex] are reported which exhibit: i) hydrolytic stability; ii) water solubility; iii) N-substitution to block peptidase hydrolysis. The first compound, N,N',N"- trimethyl-N,N',N"-tris(2,3-dihydroxysulfobenzoyl)1,3,5-triaminomethyl- benzene, [Me3MECAMS, 6] was prepared from the amide of trimesloyl chloride (1) and MeNH2. The resulting amide was reduced to the triamine (3) and converted in three steps to the final product 6 in 6% overall yield. The proton-dependent formation constant (log K*) for the reaction: Fe3+ + H3L6- = FeL6- + 3H+ is 4.87, which gives an equilibrium concentration of [Fe3+] at pH 7.4 of 2 x 10-27 M for 10-5 M L (6) and 10-6 M total Fe3+. The estimated formation constant (log β110) is 40. At low pH the FeL6- complex undergoes a series of three, one-proton reactions which probably gives a tris-salicylate complex formed by the carbonyl and ortho-catechol oxygen of the 2,3-dihydroxybenzoyl units (the same reaction that occurs with ferric enterobactin). After six hours in the presence of 6 mM ascorbate, Me3MECAMS (6.0 mM) removed 3.7% of the ferric ion initially sequestered by the iron storage protein, ferritin. The human iron transport protein transferrin gives up iron to Me3MECAMS with a pseudo first-order rate constant of 1.9 x 10-3min-1 (ligand concentration 2 X 10-4 M). This rate is comparable to that of enterobactin and other catechoyl amide sequestering agents, and greatly exceeds that of desferrioxamine B (Desferal®), the current drug of choice in treating iron

  17. Solvent substitution

    Energy Technology Data Exchange (ETDEWEB)

    1990-01-01

    The DOE Environmental Restoration and Waste Management Office of Technology Development and the Air Force Engineering and Services Center convened the First Annual International Workshop on Solvent Substitution on December 4--7, 1990. The primary objectives of this joint effort were to share information and ideas among attendees in order to enhance the development and implementation of required new technologies for the elimination of pollutants associated with industrial use of hazardous and toxic solvents; and to aid in accelerating collaborative efforts and technology transfer between government and industry for solvent substitution. There were workshop sessions focusing on Alternative Technologies, Alternative Solvents, Recovery/Recycling, Low VOC Materials and Treatment for Environmentally Safe Disposal. The 35 invited papers presented covered a wide range of solvent substitution activities including: hardware and weapons production and maintenance, paint stripping, coating applications, printed circuit boards, metal cleaning, metal finishing, manufacturing, compliance monitoring and process control monitoring. This publication includes the majority of these presentations. In addition, in order to further facilitate information exchange and technology transfer, the US Air Force and DOE solicited additional papers under a general Call for Papers.'' These papers, which underwent review and final selection by a peer review committee, are also included in this combined Proceedings/Compendium. For those involved in handling, using or managing hazardous and toxic solvents, this document should prove to be a valuable resource, providing the most up-to-date information on current technologies and practices in solvent substitution. Individual papers are abstracted separated.

  18. Revisiting fifth forces in the Galileon model

    Energy Technology Data Exchange (ETDEWEB)

    Burrage, Clare [Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany). Gruppe Theorie; Seery, David [Sussex Univ., Brighton (United Kingdom). Dept. of Physics and Astronomy

    2010-05-15

    A Galileon field is one which obeys a spacetime generalization of the non- relativistic Galilean invariance. Such a field may possess non-canonical kinetic terms, but ghost-free theories with a well-defined Cauchy problem exist, constructed using a finite number of relevant operators. The interactions of this scalar with matter are hidden by the Vainshtein effect, causing the Galileon to become weakly coupled near heavy sources. We revisit estimates of the fifth force mediated by a Galileon field, and show that the parameters of the model are less constrained by experiment than previously supposed. (orig.)

  19. Revisiting the Okun relationship

    NARCIS (Netherlands)

    Dixon, R. (Robert); Lim, G.C.; J.C. van Ours (Jan)

    2017-01-01

    textabstractOur article revisits the Okun relationship between observed unemployment rates and output gaps. We include in the relationship the effect of labour market institutions as well as age and gender effects. Our empirical analysis is based on 20 OECD countries over the period 1985–2013. We

  20. Revisiting Okun's Relationship

    NARCIS (Netherlands)

    Dixon, R.; Lim, G.C.; van Ours, Jan

    2016-01-01

    Our paper revisits Okun's relationship between observed unemployment rates and output gaps. We include in the relationship the effect of labour market institutions as well as age and gender effects. Our empirical analysis is based on 20 OECD countries over the period 1985-2013. We find that the

  1. Random eigenvalue problems revisited

    Indian Academy of Sciences (India)

    Several studies have been conducted on this topic since the mid-sixties. The. A list of .... Random eigenvalue problems revisited. 297 and various elements of Hij ,i ≤ j are statistically independent and Gaussian. The pdf of H can be expressed as, ...... Generality of this result however remains to be verified in future studies.

  2. Revisiting Professional Teacher Standards

    Science.gov (United States)

    Watson, Amanda

    2016-01-01

    The Australian Society for Music Education's (ASME) involvement in the development of professional standards for music educators was a significant and active research time in the history of the Society. As ASME celebrates its golden jubilee, it is appropriate to revisit that history and consider the future prospects of subject-specific standards.…

  3. Revisiting city connectivity

    NARCIS (Netherlands)

    Mans, U.

    2014-01-01

    This article introduces a new perspective on city connectivity in order to analyze non-hub cities and their position in the world economy. The author revisits the different approaches discussed in the Global Commodity Chains (GCC), Global Production Networks (GPN) and World City Network (WCN)

  4. The Faraday effect revisited

    DEFF Research Database (Denmark)

    Cornean, Horia; Nenciu, Gheorghe

    2009-01-01

    This paper is the second in a series revisiting the (effect of) Faraday rotation. We formulate and prove the thermodynamic limit for the transverse electric conductivity of Bloch electrons, as well as for the Verdet constant. The main mathematical tool is a regularized magnetic and geometric...

  5. Revisiting a classic: the Parker-Moffatt problem

    CERN Document Server

    Pezzi, O; Servidio, S; Valentini, F; Vasconez, C L; Yang, Y; Malara, F; Matthaeus, W H; Veltri, P

    2016-01-01

    The interaction of two colliding Alfv\\'en wave packets is here described by means of magnetohydrodynamics (MHD) and hybrid kinetic numerical simulations. The MHD evolution revisits the theoretical insights described by Moffatt, Parker, Kraichnan, Chandrasekhar and Els\\"asser in which the oppositely propagating large amplitude wave packets interact for a finite time, initiating turbulence. However, the extension to include compressive and kinetic effects, while maintaining the gross characteristics of the simpler classic formulation, also reveals intriguing features which go beyond the pure MHD treatment.

  6. Dissipation in relativistic pair-plasma reconnection: revisited

    Science.gov (United States)

    Zenitani, Seiji

    2018-01-01

    Basic properties of relativistic magnetic reconnection in electron–positron pair plasmas are investigated by using a particle-in-cell (PIC) simulation. We first revisit a problem by Hesse and Zenitani (2007 Phys. Plasmas 14 112102), who examined the kinetic Ohm’s law across the X line. We formulate a relativistic Ohm’s law by decomposing the stress–energy tensor. Then, the role of the new term, called the heat-flow inertial term, is examined in the PIC simulation data. We further evaluate the energy balance in the reconnection system. These analyses demonstrate physically transparent ways to diagnose relativistic kinetic data.

  7. REVISITING A CLASSIC: THE PARKER–MOFFATT PROBLEM

    Energy Technology Data Exchange (ETDEWEB)

    Pezzi, O.; Servidio, S.; Valentini, F.; Malara, F.; Veltri, P. [Dipartimento di Fisica, Università della Calabria, 87036 Rende (CS) (Italy); Parashar, T. N.; Yang, Y.; Matthaeus, W. H. [Department of Physics and Astronomy, University of Delaware, DE 19716 (United States); Vásconez, C. L. [Departamento de Física, Escuela Politécnica Nacional, Quito (Ecuador)

    2017-01-10

    The interaction of two colliding Alfvén wave packets is described here by means of magnetohydrodynamics (MHD) and hybrid kinetic numerical simulations. The MHD evolution revisits the theoretical insights described by Moffatt, Parker, Kraichnan, Chandrasekhar, and Elsässer in which the oppositely propagating large-amplitude wave packets interact for a finite time, initiating turbulence. However, the extension to include compressive and kinetic effects, while maintaining the gross characteristics of the simpler classic formulation, also reveals intriguing features that go beyond the pure MHD treatment.

  8. Simple, heart-smart substitutions

    Science.gov (United States)

    Coronary artery disease - heart smart substitutions; Atherosclerosis - heart smart substitutions; Cholesterol - heart smart substitutions; Coronary heart disease - heart smart substitutions; Healthy diet - heart ...

  9. Revisiting Lambert's Problem

    OpenAIRE

    Izzo, Dario

    2014-01-01

    The orbital boundary value problem, also known as Lambert Problem, is revisited. Building upon Lancaster and Blanchard approach, new relations are revealed and a new variable representing all problem classes, under L-similarity, is used to express the time of flight equation. In the new variable, the time of flight curves have two oblique asymptotes and they mostly appear to be conveniently approximated by piecewise continuous lines. We use and invert such a simple approximation to provide an...

  10. Deterministic Graphical Games Revisited

    DEFF Research Database (Denmark)

    Andersson, Daniel; Hansen, Kristoffer Arnsfelt; Miltersen, Peter Bro

    2008-01-01

    We revisit the deterministic graphical games of Washburn. A deterministic graphical game can be described as a simple stochastic game (a notion due to Anne Condon), except that we allow arbitrary real payoffs but disallow moves of chance. We study the complexity of solving deterministic graphical...... games and obtain an almost-linear time comparison-based algorithm for computing an equilibrium of such a game. The existence of a linear time comparison-based algorithm remains an open problem....

  11. Demographic Dividends Revisited

    OpenAIRE

    Jeffrey G. Williamson

    2013-01-01

    This paper revisits demographic dividend issues after almost 2 decades of debate. In 1998, David Bloom and I used a convergence model to estimate the impact of demographic-transition-driven age structure effects and calculated what the literature has come to call the “demographic dividend.” These early estimates seem to be similar to those coming from more recent overlapping generation models, when properly estimated. Research has shown that the demographic dividend is not simply a labor part...

  12. Clinical ethics revisited

    Directory of Open Access Journals (Sweden)

    Pellegrino Edmund D

    2001-04-01

    Full Text Available Abstract A decade ago, we reviewed the field of clinical ethics; assessed its progress in research, education, and ethics committees and consultation; and made predictions about the future of the field. In this article, we revisit clinical ethics to examine our earlier observations, highlight key developments, and discuss remaining challenges for clinical ethics, including the need to develop a global perspective on clinical ethics problems.

  13. Electrostatic instabilities in a mirror trap revisited

    Science.gov (United States)

    Kotelnikov, Igor A.; Chernoshtanov, Ivan S.; Prikhodko, Vadim V.

    2017-12-01

    The conditions for the stabilization of the Drift-Cyclotron Loss-Cone (DCLC) and Double-Humped (DH) microinstabilities in a mirror trap are critically revisited assuming the plasma is confined in the kinetic regime, which is characterized by an empty loss cone. The temperature of warm ions, necessary for stabilization of the DH instability, is calculated. The fraction of warm ions necessary to stabilize the DCLC instability at a given radial density gradient is calculated. Assuming the wavelength is much shorter than the Larmor radius, a simple criterion for the stability of drift-cyclotron loss-cone oscillations is derived whose accuracy is verified by comparison with the solution of the exact dispersion equation and with known experimental data obtained in the past decades in PR-6, 2XII, 2XIIB, TMX, and TMX-U devices for plasma confinement.

  14. Revisiting and Renegotiating Wars

    DEFF Research Database (Denmark)

    Gade, Solveig

    2014-01-01

    Anri Sala’s film 1395 Days Without Red (2011) provides a kind of reenactment of an accidental day during the 1992-95 siege of Sarajevo. Shot in today’s Sarajevo, the film revisits and embodies some of the widely circulated images of the siege, such as inhabitants sprinting across so-called Sniper...... Alley in order to avoid the bullets of the Bosnian Serbian snipers positioned around the city. Based on a close reading of Sala’s work, this article will scrutinize how subjectivating techniques of power, during times of war, affectively work to create boundaries between those excluded from and those...

  15. Bottomonium spectrum revisited

    CERN Document Server

    Segovia, Jorge; Entem, David R.; Fernández, Francisco

    2016-01-01

    We revisit the bottomonium spectrum motivated by the recently exciting experimental progress in the observation of new bottomonium states, both conventional and unconventional. Our framework is a nonrelativistic constituent quark model which has been applied to a wide range of hadronic observables from the light to the heavy quark sector and thus the model parameters are completely constrained. Beyond the spectrum, we provide a large number of electromagnetic, strong and hadronic decays in order to discuss the quark content of the bottomonium states and give more insights about the better way to determine their properties experimentally.

  16. Thermal degradation kinetics and solid state, temperature ...

    Indian Academy of Sciences (India)

    WINTEC

    Phenothiazine derivatives belong to a big group of aromatic compounds. These derivatives are substituted in ... Elemental analysis for carbon, hydrogen, nitrogen and sulphur were done using Vario EL III CHNS ... The aim of the kinetic study of thermal analysis data is to find out the most probable kinetic model which best ...

  17. Substitute family care

    OpenAIRE

    Petrů, Jaroslava

    2015-01-01

    The bachelor thesis focuses on substitute family care in the Czech Republic and its importance for the child. The theoretical part defines the basic terms, describes history and the forms of substitute family care. It also deals with the process of placing a child in substitute family care, the preparation of foster parents and the legislation regulating substitute family care. The practical part is based on qualitative research in families with children in foster and tutelary care, in famili...

  18. Kinetic Typography

    DEFF Research Database (Denmark)

    van Leeuwen, Theo; Djonov, Emilia

    2014-01-01

    After discussing broad cultural drivers behind the development of kinetic typography, the chapter outlines an approach to analysing kinetic typography which is based on Halliday's theory of transitivity, as applied by Kress and Van Leeuwen to visual images....

  19. Revisiting Lambert's problem

    Science.gov (United States)

    Izzo, Dario

    2015-01-01

    The orbital boundary value problem, also known as Lambert problem, is revisited. Building upon Lancaster and Blanchard approach, new relations are revealed and a new variable representing all problem classes, under L-similarity, is used to express the time of flight equation. In the new variable, the time of flight curves have two oblique asymptotes and they mostly appear to be conveniently approximated by piecewise continuous lines. We use and invert such a simple approximation to provide an efficient initial guess to an Householder iterative method that is then able to converge, for the single revolution case, in only two iterations. The resulting algorithm is compared, for single and multiple revolutions, to Gooding's procedure revealing to be numerically as accurate, while having a significantly smaller computational complexity.

  20. Logistics Innovation Process Revisited

    DEFF Research Database (Denmark)

    Gammelgaard, Britta; Su, Shong-Iee Ivan; Yang, Su-Lan

    2011-01-01

    Purpose – The purpose of this paper is to learn more about logistics innovation processes and their implications for the focal organization as well as the supply chain, especially suppliers. Design/methodology/approach – The empirical basis of the study is a longitudinal action research project...... that was triggered by the practical needs of new ways of handling material flows of a hospital. This approach made it possible to revisit theory on logistics innovation process. Findings – Apart from the tangible benefits reported to the case hospital, five findings can be extracted from this study: the logistics...... on internal stakeholders as on external relationships; and logistics innovation process may start out as a dialectic, conflict ridden process and end up in a well-ordered goal-oriented teleological process. Research limitations/implications – In general, the study contributes to the knowledge base...

  1. Deterministic Graphical Games Revisited

    DEFF Research Database (Denmark)

    Andersson, Klas Olof Daniel; Hansen, Kristoffer Arnsfelt; Miltersen, Peter Bro

    2012-01-01

    Starting from Zermelo’s classical formal treatment of chess, we trace through history the analysis of two-player win/lose/draw games with perfect information and potentially infinite play. Such chess-like games have appeared in many different research communities, and methods for solving them......, such as retrograde analysis, have been rediscovered independently. We then revisit Washburn’s deterministic graphical games (DGGs), a natural generalization of chess-like games to arbitrary zero-sum payoffs. We study the complexity of solving DGGs and obtain an almost-linear time comparison-based algorithm...... for finding optimal strategies in such games. The existence of a linear time comparison-based algorithm remains an open problem....

  2. Automated HAZOP revisited

    DEFF Research Database (Denmark)

    Taylor, J. R.

    2017-01-01

    Hazard and operability analysis (HAZOP) has developed from a tentative approach to hazard identification for process plants in the early 1970s to an almost universally accepted approach today, and a central technique of safety engineering. Techniques for automated HAZOP analysis were developed...... in the 1970s, but still have not displaced expensive manual approaches. Reasons for this were investigated and conclusions are drawn. The author's actual experience in applying automated HAZOP techniques over a period of more than 30 years is revisited, including results from several full-scale validation...... studies and many industrial applications. Automated techniques, when combined with manual approaches, were found to provide significant improvements in HAZOP quality and a limited but valuable improvement in efficiency....

  3. Revisiting the schism.

    Science.gov (United States)

    Litsios, Socrates

    2014-01-01

    The schism between medicine and public health has deep historical roots. The Rockefeller Foundation's Clinical Epidemiology program, initiated in the late 1970s, was seen by Kerr White, its director, as the means to heal the schism. This article revisits the role that the Foundation played in creating that schism before reviewing post-World War II efforts on the part of both the Foundation and the World Health Organization to incorporate the teaching of preventive medicine in medical education curricula. White labeled these efforts as failures, but a closer look at the history raises questions concerning what evidence he used to make this judgment and whether clinical epidemiology has not instead widened the gap between cure and prevention.

  4. Reframing in dentistry: Revisited

    Directory of Open Access Journals (Sweden)

    Sivakumar Nuvvula

    2013-01-01

    Full Text Available The successful practice of dentistry involves a good combination of technical skills and soft skills. Soft skills or communication skills are not taught extensively in dental schools and it can be challenging to learn and at times in treating dental patients. Guiding the child′s behavior in the dental operatory is one of the preliminary steps to be taken by the pediatric dentist and one who can successfully modify the behavior can definitely pave the way for a life time comprehensive oral care. This article is an attempt to revisit a simple behavior guidance technique, reframing and explain the possible psychological perspectives behind it for better use in the clinical practice.

  5. Medicineringsfejl ved generisk substitution

    DEFF Research Database (Denmark)

    Rölfing, Jan

    2012-01-01

    Generic substitution is a major cause of medical mistakes in the general population. Danish legislation obligates pharmacies to substitute prescribed medicine with the cheapest equivalent formulation, despite variations in product name, packaging, shape and colour. Consequently, medical mistakes...... occur. Scientific evidence on the consequences of generic substitution is sparse. Call upon fellow health workers to report medical mistakes to the national entities and scientific peers, in order to increase awareness and scientific evidence about the problem....

  6. Synthesis, computational studies and enzyme inhibitory kinetics of substituted methyl[2-(4-dimethylamino-benzylidene)-hydrazono)-4-oxo-thiazolidin-5-ylidene]acetates as mushroom tyrosinase inhibitors.

    Science.gov (United States)

    Channar, Pervaiz Ali; Saeed, Aamer; Larik, Fayaz Ali; Rafiq, Muhammad; Ashraf, Zaman; Jabeen, Farukh; Fattah, Tanzeela Abdul

    2017-11-01

    The present article describes the synthesis and enzyme inhibitory kinetics of methyl[2-(arylmethylene-hydrazono)-4-oxo-thiazolidin-5-ylidene]acetates 5a-j as mushroom tyrosinase inhibitors. The title compounds were synthesized via cyclocondensation of thiosemicarbazones 3a-j with dimethyl but-2-ynedioate (DMAD) 4 in good yields under solvent-free conditions. The synthesized compounds were evaluated for their potential to inhibit the activity of mushroom tyrosinase. It was unveiled that compounds 5i showed excellent enzyme inhibitory activity with IC 50 3.17µM while IC 50 of standard kojic acid is 15.91µM. The presence of heterocyclic pyridine ring in compound 5i play important role in enzyme inhibitory activity as rest of the functional groups are common in all synthesized compounds. The enzyme inhibitory kinetics of the most potent derivative 5i determined by Lineweaver-Burk plots and Dixon plots showed that it is non-competitive inhibitor with Ki value 1.5µM. It was further investigated that the wet lab results are in good agreement with the computational results. The molecular docking of the synthesized compounds was performed against tyrosinase protein (PDBID 2Y9X) to delineate ligand-protein interactions at molecular level. The docking results showed that the major interacting residues are His244, His85, His263, Val 283, His 296, Asn260, Val248, His260, His261 and Phe264 which are located in active binding site of the protein. The molecular modeling demonstrates that the oxygen atom of the compound 5i coordinated with the key residues in the active site of mushroom tyrosinase contribute significantly against inhibitory ability and diminishing the human melanin synthesis. These results evident that compound 5i is a lead structure in developing most potent mushroom tyrosinase inhibitors. Copyright © 2017 Elsevier Ltd. All rights reserved.

  7. Sustainability and substitutability.

    Science.gov (United States)

    Fenichel, Eli P; Zhao, Jinhua

    2015-02-01

    Developing a quantitative science of sustainability requires bridging mathematical concepts from fields contributing to sustainability science. The concept of substitutability is central to sustainability but is defined differently by different fields. Specifically, economics tends to define substitutability as a marginal concept while fields such as ecology tend to focus on limiting behaviors. We explain how to reconcile these different views. We develop a model where investments can be made in knowledge to increase the elasticity of substitution. We explore the set of sustainable and optimal trajectories for natural capital extraction and built and knowledge capital accumulation. Investments in substitutability through knowledge stock accumulation affect the value of natural capital. Results suggest that investing in the knowledge stock, which can enhance substitutability, is critical to desirable sustainable outcomes. This result is robust even when natural capital is not managed optimally. This leads us to conclude that investments in the knowledge stock are of first order importance for sustainability.

  8. Lorentz violation naturalness revisited

    Energy Technology Data Exchange (ETDEWEB)

    Belenchia, Alessio; Gambassi, Andrea; Liberati, Stefano [SISSA - International School for Advanced Studies, via Bonomea 265, 34136 Trieste (Italy); INFN, Sezione di Trieste, via Valerio 2, 34127 Trieste (Italy)

    2016-06-08

    We revisit here the naturalness problem of Lorentz invariance violations on a simple toy model of a scalar field coupled to a fermion field via a Yukawa interaction. We first review some well-known results concerning the low-energy percolation of Lorentz violation from high energies, presenting some details of the analysis not explicitly discussed in the literature and discussing some previously unnoticed subtleties. We then show how a separation between the scale of validity of the effective field theory and that one of Lorentz invariance violations can hinder this low-energy percolation. While such protection mechanism was previously considered in the literature, we provide here a simple illustration of how it works and of its general features. Finally, we consider a case in which dissipation is present, showing that the dissipative behaviour does not percolate generically to lower mass dimension operators albeit dispersion does. Moreover, we show that a scale separation can protect from unsuppressed low-energy percolation also in this case.

  9. Lipase-catalyzed domino kinetic resolution/intramolecular Diels-Alder reaction: one-pot synthesis of optically active 7-oxabicyclo[2.2.1]heptenes from furfuryl alcohols and beta-substituted acrylic acids.

    Science.gov (United States)

    Akai, Shuji; Naka, Tadaatsu; Omura, Sohei; Tanimoto, Kouichi; Imanishi, Masashi; Takebe, Yasushi; Matsugi, Masato; Kita, Yasuyuki

    2002-09-16

    The first lipase-catalyzed domino reaction is described in which the acyl moiety formed during the enzymatic kinetic resolution of furfuryl alcohols (+/-)-3 with a 1-ethoxyvinyl ester 2 was utilized as a part of the constituent structure for the subsequent Diels-Alder reaction. The preparation of ester 2 from carboxylic acid 1 and the subsequent domino reaction were carried out in a one-pot reaction. Therefore, this procedure provides a convenient preparation of the optically active 7-oxabicyclo[2.2.1]heptene derivatives 5, which has five chiral, non-racemic carbon centers, from achiral 1 and racemic 3. The overall efficiency of this process was dependent on the substituent at the C-3 position of 3, and the use of the 3-methylfurfuryl derivatives, (+/-)-3 b and (+/-)-3 f, exclusively produced diastereoselectivity with excellent enantioselectivity to give (2R)-syn-5 (91->/=99 % ee) and (S)-3 (96->/=99 % ee). Similar procedures starting from the 3-bromofurfuryl alcohols (+/-)-3 h-j provided the cycloadducts (2R)-syn-5 j-q (93->/=99 % ee), in which the bromo group was utilized for the installation of bulky substituents to the 7-oxabicycloheptene core.

  10. The "Mushroom Cloud" Demonstration Revisited

    Science.gov (United States)

    Panzarasa, Guido; Sparnacci, Katia

    2013-01-01

    A revisitation of the classical "mushroom cloud" demonstration is described. Instead of aniline and benzoyl peroxide, the proposed reaction involves household chemicals such as alpha-pinene (turpentine oil) and trichloroisocyanuric acid ("Trichlor") giving an impressive demonstration of oxidation and combustion reactions that…

  11. Leadership and Management Theories Revisited

    DEFF Research Database (Denmark)

    Madsen, Mona Toft

    2001-01-01

    The goal of the paper is to revisit and analyze key contributions to the understanding of leadership and management. As a part of the discussion a role perspective that allows for additional and/or integrated leader dimensions, including a change-centered, will be outlined. Seemingly, a major...

  12. Revisiting Inter-Genre Similarity

    DEFF Research Database (Denmark)

    Sturm, Bob L.; Gouyon, Fabien

    2013-01-01

    We revisit the idea of ``inter-genre similarity'' (IGS) for machine learning in general, and music genre recognition in particular. We show analytically that the probability of error for IGS is higher than naive Bayes classification with zero-one loss (NB). We show empirically that IGS does...

  13. A remote coal deposit revisited

    DEFF Research Database (Denmark)

    Bojesen-Kofoed, Jørgen A.; Kalkreuth, Wolfgang; Petersen, Henrik I.

    2012-01-01

    In 1908, members of the “Danmark Expedition” discovered a coal deposit in a very remote area in western Germania Land, close to the margin of the inland ice in northeast Greenland. The deposit was, however, neither sampled nor described, and was revisited in 2009 for the first time since its...

  14. Benjamin Franklin and Mesmerism, revisited.

    Science.gov (United States)

    McConkey, Kevin M; Perry, Campbell

    2002-10-01

    The authors revisit and update their previous historiographical note (McConkey & Perry, 1985) on Benjamin Franklin's involvement with and investigation of animal magnetism or mesmerism. They incorporate more recent literature and offer additional comment about Franklin's role in and views about mesmerism. Franklin had a higher degree of personal involvement with and a more detailed opinion of mesmerism than has been previously appreciated.

  15. Revisiting the Kinetics and Mechanism of Bromate-Bromide Reaction

    Directory of Open Access Journals (Sweden)

    Côrtes Carlos Eduardo S.

    2001-01-01

    Full Text Available The bromate-bromide reaction was investigated in an acidity range not studied yet. The reaction was followed at the Br2/Br3- isosbestic point (lambda = 446 nm. It was observed a first-order behavior for bromate and bromide ions and a second-order behavior for H+ ion that results in the rate law nu = k[BrO3-][Br- ][H+]². This rate law suggests a mechanism involving two successive protonation of bromate followed by the interaction of the intermediate species H2BrO3+ with bromide. These results disagree with the obtained by other authors who observed a second-order behavior for the bromide and first-order for H+, and have proposed intermediate species like H2Br2O3 and HBr2O3-. The second-order for [H+] observed in the range 0.005 <= [H+] <= 2.77 mol L-1 sets down that the pKa of bromic acid, HBrO3, must be lower than -0.5 (T = 25 °C, different from all other values for this pKa proposed in the literature.

  16. Kinetic Interface

    DEFF Research Database (Denmark)

    2009-01-01

    A kinetic interface for orientation detection in a video training system is disclosed. The interface includes a balance platform instrumented with inertial motion sensors. The interface engages a participant's sense of balance in training exercises.......A kinetic interface for orientation detection in a video training system is disclosed. The interface includes a balance platform instrumented with inertial motion sensors. The interface engages a participant's sense of balance in training exercises....

  17. n'-(substituted phenyl)

    African Journals Online (AJOL)

    Preferred Customer

    cyano-3-methyl thioacrylyl)-N'-(substituted phenyl)urea (5). Benzylamine attacked double bond to form a transition state in which the orientation of benzylamino and ester carbonyl is cis because of the formation of an intramolecular hydrogen.

  18. Synthesis of substituted pyrazines

    Science.gov (United States)

    Pagoria, Philip F.; Zhang, Mao Xi

    2016-10-04

    A method for synthesizing a pyrazine-containing material according to one embodiment includes contacting an iminodiacetonitrile derivative with a base and a reagent selected from a group consisting of hydroxylamine, a hydroxylamine salt, an aliphatic primary amine, a secondary amine, an aryl-substituted alkylamine a heteroaryl-substituted alkyl amine, an alcohol, an alkanolamine and an aryl alcoholamine. Additional methods and several reaction products are presented. ##STR00001##

  19. Revisiting Tversky's diagnosticity principle.

    Science.gov (United States)

    Evers, Ellen R K; Lakens, Daniël

    2014-01-01

    Similarity is a fundamental concept in cognition. In 1977, Amos Tversky published a highly influential feature-based model of how people judge the similarity between objects. The model highlights the context-dependence of similarity judgments, and challenged geometric models of similarity. One of the context-dependent effects Tversky describes is the diagnosticity principle. The diagnosticity principle determines which features are used to cluster multiple objects into subgroups. Perceived similarity between items within clusters is expected to increase, while similarity between items in different clusters decreases. Here, we present two pre-registered replications of the studies on the diagnosticity effect reported in Tversky (1977). Additionally, one alternative mechanism that has been proposed to play a role in the original studies, an increase in the choice for distractor items (a substitution effect, see Medin et al., 1995), is examined. Our results replicate those found by Tversky (1977), revealing an average diagnosticity-effect of 4.75%. However, when we eliminate the possibility of substitution effects confounding the results, a meta-analysis of the data provides no indication of any remaining effect of diagnosticity.

  20. Remembered Experiences and Revisit Intentions

    DEFF Research Database (Denmark)

    Barnes, Stuart; Mattsson, Jan; Sørensen, Flemming

    2016-01-01

    Tourism is an experience-intensive sector in which customers seek and pay for experiences above everything else. Remembering past tourism experiences is also crucial for an understanding of the present, including the predicted behaviours of visitors to tourist destinations. We adopt a longitudinal...... approach to memory data collection from psychological science, which has the potential to contribute to our understanding of tourist behaviour. In this study, we examine the impact of remembered tourist experiences in a safari park. In particular, using matched survey data collected longitudinally and PLS...... path modelling, we examine the impact of positive affect tourist experiences on the development of revisit intentions. We find that longer-term remembered experiences have the strongest impact on revisit intentions, more so than predicted or immediate memory after an event. We also find that remembered...

  1. Leadership and Management Theories Revisited

    OpenAIRE

    Madsen, Mona Toft

    2001-01-01

    The goal of the paper is to revisit and analyze key contributions to the understanding of leadership and management. As a part of the discussion a role perspective that allows for additional and/or integrated leader dimensions, including a change-centered, will be outlined. Seemingly, a major challenge on the substantive level is the integration of soft and hard managerial functions, while the concepts used in presenting these should at least in transition be able to contain a distinction bet...

  2. Revisiting Nursing Research in Nigeria

    OpenAIRE

    Emelonye A.U; Pitkäaho T; Aregbesola A; Vehviläinen- Julkunen K

    2016-01-01

    Background: Evidence from a nursing conference convened in Nigeria in 1973 amongst other things implied that Nigerian nurses are not adequately educated and ill-equipped with prerequisite research skills. Four decades after the first and only initiative that examined the capacity and contribution of Nigerian Nurses to health care research, it is therefore pertinent to revisit the state of nursing research in the country. Aim: To review the academic and research preparedness of ...

  3. Kinetics and

    Directory of Open Access Journals (Sweden)

    Mojtaba Ahmadi

    2016-11-01

    Full Text Available The aqueous degradation of Reactive Yellow 84 (RY84 by potassium peroxydisulfate (K2S2O8 has been studied in laboratory scale experiments. The effect of the initial concentrations of potassium peroxydisulfate and RY84, pH and temperature on RY84 degradation were also examined. Experimental data were analyzed using first and second-order kinetics. The degradation kinetics of RY84 of the potassium peroxydisulfate process followed the second-order reaction kinetics. These rate constants have an extreme values similar to of 9.493 mM−1min−1 at a peroxydisulfate dose of 4 mmol/L. Thermodynamic parameters such as activation (Ea and Gibbs free energy (ΔG° were also evaluated. The negative value of ΔGo and Ea shows the spontaneous reaction natural conditions and exothermic nature.

  4. Bone substitute biomaterials

    CERN Document Server

    Mallick, K

    2014-01-01

    Bone substitute biomaterials are fundamental to the biomedical sector, and have recently benefitted from extensive research and technological advances aimed at minimizing failure rates and reducing the need for further surgery. This book reviews these developments, with a particular focus on the desirable properties for bone substitute materials and their potential to encourage bone repair and regeneration. Part I covers the principles of bone substitute biomaterials for medical applications. One chapter reviews the quantification of bone mechanics at the whole-bone, micro-scale, and non-scale levels, while others discuss biomineralization, osteoductivization, materials to fill bone defects, and bioresorbable materials. Part II focuses on biomaterials as scaffolds and implants, including multi-functional scaffolds, bioceramics, and titanium-based foams. Finally, Part III reviews further materials with the potential to encourage bone repair and regeneration, including cartilage grafts, chitosan, inorganic poly...

  5. [Delegation yes, substitution no!].

    Science.gov (United States)

    Schroeder, A

    2014-08-01

    The aging of society leads on the one hand to increasing case numbers and on the other hand to a reduction in the number of physicians available for patient treatment. The delegation and substitution of medical duties as a tried and tested method is increasingly being recommended in order to compensate for the lack of physicians. The Berufsverband der Deutschen Urologen (BDU, Professional Association of German Urologists) supports the guiding principle of the Bundesärztekammer (Federal Medical Council) of "delegation yes, substitution no" and rejects a substitution of medical duties by non-medical academic health personnel. Against the background of the demographic changes, the increasing need for treatment and the current deficiency of junior physicians, a more extensive inclusion of well-qualified and experienced non-medical personnel by the delegation of medically responsible duties (medical scope of practice) can be an appropriate measure to maintain a good medical service in practices, hospitals and nursing homes.

  6. Computational study of vicarious nucleophilic substitution reactions.

    Science.gov (United States)

    Meneses, Lorena; Morocho, Shirley; Castellanos, Alejandra; Cuesta, Sebastián

    2017-10-02

    Vicarious nucleophilic substitution reactions are a versatile way of introducing substituents into aromatic and heteroaromatic electron-deficient compounds. In this project, a kinetic study of these reactions by applying quantum mechanics concepts, such as reaction force, force constant, and electronic reaction flow was proposed. Furthermore, absolute theoretical scales of electrophilicity by applying density functional theory electronic indices were established to classify a series of five and six-membered nitroheteroarenes, and nitrobenzenes with substituents in ortho, meta and para positions. The theoretical model was validated by comparison with experimental kinetic results. Calculations using B3LYP/6-311G(d,p) level of theory allowed analysis of the reactivity patterns and the mechanisms of these chemical reactions. The theoretical scale properly accounts for the activating/deactivating effects promoted by the substituents and agrees with the ability of these substituents to accept or donate electrons, electron acceptor substituents are those that increase electrophilicity, and electron donors those that reduce it.

  7. Revisiting Johnson and Jackson boundary conditions for granular flows

    Energy Technology Data Exchange (ETDEWEB)

    Li, Tingwen; Benyahia, Sofiane

    2012-07-01

    In this article, we revisit Johnson and Jackson boundary conditions for granular flows. The oblique collision between a particle and a flat wall is analyzed by adopting the classic rigid-body theory and a more realistic semianalytical model. Based on the kinetic granular theory, the input parameter for the partial-slip boundary conditions, specularity coefficient, which is not measurable in experiments, is then interpreted as a function of the particle-wall restitution coefficient, the frictional coefficient, and the normalized slip velocity at the wall. An analytical expression for the specularity coefficient is suggested for a flat, frictional surface with a low frictional coefficient. The procedure for determining the specularity coefficient for a more general problem is outlined, and a working approximation is provided.

  8. Performing Substitute Teaching

    Science.gov (United States)

    Bletzer, Keith V.

    2010-01-01

    Formal education is both a right and an obligation bestowed on young people in most all nations of the world. Teachers (adults) and students (youth) form a co-present dyadic contract that must be maintained within the classroom. Substitute teachers fill a role in sustaining the integrity of this teacher-student link, whenever teachers are absent.…

  9. n'-(substituted phenyl)

    African Journals Online (AJOL)

    Preferred Customer

    5h),. 4-F (5i), 2, 4-F (5j), 4-F-3-Cl (5k). Scheme 1. Schematic representation of the preparation of N-(3-benzylamino-2-cyano-3-methyl thioacrylyl)-N'-(substituted phenyl)urea (5). Benzylamine attacked double bond to form a transition state in ...

  10. KINETICS OF SUBSTITUTION OF CIS-BIS(MALONATO ...

    African Journals Online (AJOL)

    Preferred Customer

    Effect of concentration of amino acids. The pseudo-first order rate constants were evaluated from the straight line plot of log (A∞-At) vs. time by using KINTOB software procedure. The rate of the reaction increases with increase in the concentration of amino acids (Table 1). In the amino acid variation studies the pH was kept.

  11. Kinetics and mechanism of the oxidation of substituted ...

    Indian Academy of Sciences (India)

    Unknown

    The reaction rate increases linearly with an increase in the concentration of the amine. Thus the reaction is first order with respect to amines also. Oxidation of benzylamine, in an atmosphere of nitrogen, failed to induce the polymerization of acrylonitrile. Further, the addition of acrylonitrile had no effect on the rate of ...

  12. Equilibrium and kinetic studies on ligand substitution reactions of ...

    Indian Academy of Sciences (India)

    Unknown

    cobaloxime with histamine, histidine, glycine and ethyl glycine ester were studied as a function of. pH at 25°C, 1⋅0 M ionic strength (KCl) by spectrophotometric techniques. Comparison of equilibrium constants and rate constants tells that the order is.

  13. Revisiting the Koebner Phenomenon

    Science.gov (United States)

    Raychaudhuri, Siba P.; Jiang, Wen-Yue; Raychaudhuri, Smriti K.

    2008-01-01

    Nerve growth factor (NGF) influences the key pathological events of psoriasis: keratinocyte proliferation, angiogenesis, and T-cell activation. We have systematically examined the kinetics of NGF expression, keratinocyte proliferation, and migration of T lymphocytes in the epidermis in Koebner-induced developing psoriatic plaques. In skin traumatized by the tape-stripping method (n = 12), a marked up-regulation of NGF in Koebner-positive lesions (n = 7) was observed 24 hours after trauma. Synthesis of NGF reached its maximum level in the 2nd week. Furthermore, cultured keratinocytes from nonlesional skin of psoriasis patients produced 10 times higher levels of NGF compared with keratinocytes from healthy individuals. To substantiate the in vivo effect of NGF secreted by keratinocytes in psoriatic plaques, we studied psoriatic plaques and normal human skin in a SCID-human skin xenograft model. The transplanted psoriatic plaques demonstrated marked proliferation of NGF-R (p75)-positive nerve fibers compared with only a few nerves in the transplanted normal human skin. Our results demonstrate that 1) in a developing psoriatic lesion, up-regulation of NGF together with keratinocyte proliferation are early events and precede epidermotropism of T lymphocytes; 2) keratinocytes in patients with psoriasis are primed to produce elevated levels of NGF; and 3) NGF synthesized by these keratinocytes is functionally active. PMID:18349121

  14. Configurational Entropy Revisited

    Science.gov (United States)

    Lambert, Frank L.

    2007-09-01

    Entropy change is categorized in some prominent general chemistry textbooks as being either positional (configurational) or thermal. In those texts, the accompanying emphasis on the dispersal of matter—independent of energy considerations and thus in discord with kinetic molecular theory—is most troubling. This article shows that the variants of entropy can be treated from a unified viewpoint and argues that to decrease students' confusion about the nature of entropy change these variants of entropy should be merged. Molecular energy dispersal in space is implicit but unfortunately tacit in the cell models of statistical mechanics that develop the configurational entropy change in gas expansion, fluids mixing, or the addition of a non-volatile solute to a solvent. Two factors are necessary for entropy change in chemistry. An increase in thermodynamic entropy is enabled in a process by the motional energy of molecules (that, in chemical reactions, can arise from the energy released from a bond energy change). However, entropy increase is only actualized if the process results in a larger number of arrangements for the system's energy, that is, a final state that involves the most probable distribution for that energy under the new constraints. Positional entropy should be eliminated from general chemistry instruction and, especially benefiting "concrete minded" students, it should be replaced by emphasis on the motional energy of molecules as enabling entropy change.

  15. Kinetic Biochemistry

    OpenAIRE

    Jäntschi, Lorentz

    2003-01-01

    Mathematics and computer programming have a major contribution to chemistry. Two directions can be identified: one that searches and tries (rich) to explain the structural binding and shape of the chemical compounds [1] with major applications in QSPR/QSAR studies [2], and applied sciences such as engineering of materials or agriculture [3]; the second direction is to models the kinetic processes that are involved in chemical reactions [4]. Many such models are available here. The present pap...

  16. Kinetic Biochemistry

    Directory of Open Access Journals (Sweden)

    Lorentz JÄNTSCHI

    2003-03-01

    Full Text Available Mathematics and computer programming have a major contribution to chemistry. Two directions can be identified: one that searches and tries (rich to explain the structural binding and shape of the chemical compounds [1] with major applications in QSPR/QSAR studies [2], and applied sciences such as engineering of materials or agriculture [3]; the second direction is to models the kinetic processes that are involved in chemical reactions [4]. Many such models are available here. The present paper describes three variants of well the known kinetic models and presents the mathematical equations associated with them. The differential equations are numerically solved and fitted with MathCad program. [1] Diudea M., Gutman I., Jäntschi L., Molecular Topology, Nova Science, Huntington, New York, 332 p., 2001, 2002. [2] Diudea M. V., Ed., QSPR / QSAR Studies by Molecular Descriptors, Nova Science, Huntington, New York, 438 p., 2001. [3] Jäntschi L., Microbiology and Toxicology. Phytochemistry Studies (in Romanian, Amici, Cluj-Napoca, 184 p., 2003. [4] Jäntschi L., Unguresan M., Physical Chemistry. Molecular Kinetic and Dynamic (in Romanian, Mediamira, Cluj-Napoca, 159 p., 2001.

  17. Physisorption kinetics

    CERN Document Server

    Kreuzer, Hans Jürgen

    1986-01-01

    This monograph deals with the kinetics of adsorption and desorption of molecules physisorbed on solid surfaces. Although frequent and detailed reference is made to experiment, it is mainly concerned with the theory of the subject. In this, we have attempted to present a unified picture based on the master equation approach. Physisorption kinetics is by no means a closed and mature subject; rather, in writing this monograph we intended to survey a field very much in flux, to assess its achievements so far, and to give a reasonable basis from which further developments can take off. For this reason we have included many papers in the bibliography that are not referred to in the text but are of relevance to physisorption. To keep this monograph to a reasonable size, and also to allow for some unity in the presentation of the material, we had to omit a number of topics related to physisorption kinetics. We have not covered to any extent the equilibrium properties of physisorbed layers such as structures, phase tr...

  18. The Ammonia Dimer Revisited

    Science.gov (United States)

    Dawes, Richard; Van Der Avoird, Ad

    2012-06-01

    The conclusion from microwave spectra by Nelson, Fraser, and Klemperer that the ammonia dimer has a nearly cyclic structure led to much debate about the issue of whether (NH_3)_2 is hydrogen bonded. This structure was surprising because most {ab initio} calculations led to a classical, nearly linear, hydrogen-bonded structure. An obvious explanation of the discrepancy between the outcome of these calculations and the microwave data which led Nelson {et al.} to their ``surprising structure'' might be the effect of vibrational averaging: the electronic structure calculations focus on finding the minimum of the intermolecular potential, the experiment gives a vibrationally averaged structure. Isotope substitution studies seemed to indicate, however, that the complex is nearly rigid. Additional data became available from high-resolution molecular beam far-infrared spectroscopy in the Saykally group. These spectra, displaying large tunneling splittings, indicate that the complex is very floppy. The seemingly contradictory experimental data were explained when it became possible to calculate the vibration-rotation-tunneling (VRT) states of the complex on a six-dimensional intermolecular potential surface. The potential used was a simple model potential, with parameters fitted to the far-infrared data. Now, for the first time, a six-dimensional potential was computed by high level {ab initio} methods and this potential will be used in calculations of the VRT states of (NH_3)_2 and (ND_3)_2. So, we will finally be able to answer the question whether the conclusions from the model calculations are indeed a valid explanation of the experimental data. D. Nelson, G. T. Fraser, and W. Klemperer J. Chem. Phys. 83 6201 (1985) J. G. Loeser, C. A. Schmuttenmaer, R. C. Cohen, M. J. Elrod, D. W. Steyert, R. J. Saykally, R. E. Bumgarner, and G. A. Blake J. Chem. Phys. 97 4727 (1992) E. H. T. Olthof, A. van der Avoird, and P. E. S. Wormer J. Chem. Phys. 101 8430 (1994) E. H. T. Olthof

  19. CORPORATIONS AND THE 99%: TEAM PRODUCTION REVISITED

    National Research Council Canada - National Science Library

    Shlomit Azgad-Tromer

    2015-01-01

    .... Revisiting team production analysis, this Article redefines the corporate team and argues that while several constituencies indeed form part of the corporate team, others are exogenous to the corporate enterprise...

  20. Kinetic buffers.

    Science.gov (United States)

    Alibrandi, Giuseppe; Fabbrizzi, Luigi; Licchelli, Maurizio; Puglisi, Antonio

    2015-01-12

    This paper proposes a new type of molecular device that is able to act as an inverse proton sponge to slowly decrease the pH inside a reaction vessel. This makes the automatic monitoring of the concentration of pH-sensitive systems possible. The device is a composite formed of an alkyl chloride, which kinetically produces acidity, and a buffer that thermodynamically modulates the variation in pH value. Profiles of pH versus time (pH-t plots) have been generated under various experimental conditions by computer simulation, and the device has been tested by carrying out automatic spectrophotometric titrations, without using an autoburette. To underline the wide variety of possible applications, this new system has been used to realize and monitor HCl uptake by a di-copper(II) bistren complex in a single run, in a completely automatic experiment. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. The power reinforcement framework revisited

    DEFF Research Database (Denmark)

    Nielsen, Jeppe; Andersen, Kim Normann; Danziger, James N.

    2016-01-01

    Whereas digital technologies are often depicted as being capable of disrupting long-standing power structures and facilitating new governance mechanisms, the power reinforcement framework suggests that information and communications technologies tend to strengthen existing power arrangements within...... public organizations. This article revisits the 30-yearold power reinforcement framework by means of an empirical analysis on the use of mobile technology in a large-scale programme in Danish public sector home care. It explores whether and to what extent administrative management has controlled decision......-making and gained most benefits from mobile technology use, relative to the effects of the technology on the street-level workers who deliver services. Current mobile technology-in-use might be less likely to be power reinforcing because it is far more decentralized and individualized than the mainly expert...

  2. Confidence in generic drug substitution.

    Science.gov (United States)

    Lionberger, R; Jiang, W; Huang, S-M; Geba, G

    2013-10-01

    Patients should have confidence that the generic drugs they are prescribed in the United States can be effectively substituted for the brand product or another generic product. Through new bioequivalence study designs for narrow therapeutic index (NTI) drugs and postapproval studies of generic substitution, the US Food and Drug Administration's (FDA's) ongoing generic drug regulatory science activities are designed to ensure successful generic substitution for all drug products.

  3. Sodium dopants in helium clusters: Structure, equilibrium and submersion kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Calvo, F. [Laboratoire Interdisciplinaire de Physique, Rue de La Piscine, Campus Saint Martin d’Hères, 38000 Grenoble (France)

    2015-12-31

    Alkali impurities bind to helium nanodroplets very differently depending on their size and charge state, large neutral or charged dopants being wetted by the droplet whereas small neutral impurities prefer to reside aside. Using various computational modeling tools such as quantum Monte Carlo and path-integral molecular dynamics simulations, we have revisited some aspects of the physical chemistry of helium droplets interacting with sodium impurities, including the onset of snowball formation in presence of many-body polarization forces, the transition from non-wetted to wetted behavior in larger sodium clusters, and the kinetics of submersion of small dopants after sudden ionization.

  4. Degenerate nucleophilic substitution in phosphonium salts.

    Science.gov (United States)

    Jennings, Elizabeth V; Nikitin, Kirill; Ortin, Yannick; Gilheany, Declan G

    2014-11-19

    Rates and energy barriers of degenerate halide substitution on tetracoordinate halophosphonium cations have been measured by NMR techniques (VT and EXSY) using a novel experimental design whereby a chiral substituent ((s)Bu) lifts the degeneracy of the resultant salts. Concomitantly, a viable computational approach to the system was developed to gain mechanistic insights into the structure and relative stabilities of the species involved. Both approaches strongly suggest a two-step mechanism of formation of a pentacoordinate dihalophosphorane via backside attack followed by dissociation, resulting in inversion of configuration at phosphorus. The experimentally determined barriers range from salts. Calculations determined that this was due to the easier accessibility in solution of pentacoordinate dichlorophosphoranes when compared to analogous dibromophosphoranes. In line with the proposed associative mechanism, bulky substituents slow the reaction in the order Me < Et < (i)Pr < (t)Bu. Bulky substituents affect the shape of the reaction energy profile so that the pentacoordinate intermediate is destabilized eventually becoming a transition state. The magnitude of the steric effects is comparable to that of the same substituents on substitution at primary alkyl halides, which can be rationalized by the relatively longer P-C bonds. The reaction displays first-order kinetics due to the prevalence of tight- or solvent-separated ion pairs in solution. Three-dimensional reaction potential energy profiles (More O'Ferrall-Jencks plots) indicated a relatively shallow potential well corresponding to the trigonal bipyramid intermediate flanked by two transition states.

  5. Photoinduced intramolecular substitution reaction of aryl halide with carbonyl oxygen of amide group

    Energy Technology Data Exchange (ETDEWEB)

    Park, Yong Tae; Song, Myong Geun; Kim, Moon Sub; Kwon, Jeong Hee [Kyungpook National Univ., Daegu (Korea, Republic of)

    2002-09-01

    Photoreaction of N-(o-halophenyl)acetamide in basic acetonitrile produces an intramolecular substituted product, 2-methylbenzoxazole in addition to reduced product, acetanilide, whereas photoreaction of N-(o-halobenzyl)acetamide affords a reduced product, N-benzylacetamide only. On the basis of preparative reaction, kinetics, and UV/vis absorption behavior, an electrophilic aromatic substitution of aryl halide with oxygen of its amide bond are proposed.

  6. Photoinduced intramolecular substitution reaction of aryl halide with carbonyl oxygen of amide group

    CERN Document Server

    Park, Y T; Kim, M S; Kwon, J H

    2002-01-01

    Photoreaction of N-(o-halophenyl)acetamide in basic acetonitrile produces an intramolecular substituted product, 2-methylbenzoxazole in addition to reduced product, acetanilide, whereas photoreaction of N-(o-halobenzyl)acetamide affords a reduced product, N-benzylacetamide only. On the basis of preparative reaction, kinetics, and UV/vis absorption behavior, an electrophilic aromatic substitution of aryl halide with oxygen of its amide bond are proposed.

  7. Thermal ignition revisited with molecular dynamics: role of fluctuations in activated collisions

    CERN Document Server

    Sirmas, Nick

    2016-01-01

    The problem of thermal ignition in a homogeneous gas is revisited from a molecular dynamics perspective. The simple model assumes reactive particles of type A and B in a fixed domain that react to form type C products if an activation threshold for impact is surpassed. Such a reaction liberates kinetic energy to the product particles, representative of the heat release. The results are compared with those obtained from the continuum description with the reaction rate evaluated from kinetic theory assuming local thermodynamic equilibrium and Maxwell-Boltzmann statistics, in order to assess the role played by molecular fluctuations. Results show that at low activation energies, the ignition time obtained from the molecular dynamics is independent of domain size, with values exceeding what is expected from the continuum model for all values of heat release. The ignition time was found dependent on domain size for larger activation energies. Small domains of $N=100$ particles yielded longer ignition delays than p...

  8. Currency substitution in Eastern Europe

    NARCIS (Netherlands)

    van Aarle, B.; Budina, N.

    1995-01-01

    Monetary instability during the transition process from a command economy to a market economy has induced a considerable increase in currency substitution in Eastern Europe. Currency substitution itself affects monetary stability since it reduces the stability of velocity. This paper investigates

  9. Revisiting tourist behavior via destination brand worldness

    Directory of Open Access Journals (Sweden)

    Murat Kayak

    2016-11-01

    Full Text Available Taking tourists’ perspective rather than destination offerings as its core concept, this study introduces “perceived destination brand worldness” as a variable. Perceived destination brand worldness is defined as the positive perception that a tourist has of a country that is visited by tourists from all over the world. Then, the relationship between perceived destination brand worldness and intention to revisit is analyzed using partial least squares regression. This empirical study selects Taiwanese tourists as its sample, and the results show that perceived destination brand worldness is a direct predictor of intention to revisit. In light of these empirical findings and observations, practical and theoretical implications are discussed.

  10. How Do Substitute Teachers Substitute? An Empirical Study of Substitute-Teacher Labor Supply

    Science.gov (United States)

    Gershenson, Seth

    2012-01-01

    This paper examines the daily labor supply of a potentially important, but often overlooked, source of instruction in U.S. public schools: substitute teachers. I estimate a sequential binary-choice model of substitute teachers' job-offer acceptance decisions using data on job offers made by a randomized automated calling system. Importantly, this…

  11. Personality-relationship transactions revisited.

    Science.gov (United States)

    Neyer, Franz J; Mund, Marcus; Zimmermann, Julia; Wrzus, Cornelia

    2014-12-01

    The transactional paradigm states that people create, maintain, and change their environments according to their personalities. At the same time, the environment reacts back on personality. As social relationships are part of an individual's environment, this likewise implies that there are reciprocal transactions between personality and relationships. However, earlier studies have concluded that adult personality traits are so stable that they have a stronger effect on later relationships, but that relationship effects on personality are negligible. In this article, we contend that personality-relationship transactions should be revisited. We submit that the relative powers of personality versus relationship effects depend on the type of life transition during which the effects take place: Relationship effects on personality development are more likely to emerge in the context of rather normative and highly scripted life transitions, whereas personality effects on relationship development are more likely to occur in the context of rather non-normative life transitions that are less regulated by social expectations. We illustrate these assumptions with examples from our own work and other findings reported in the literature. Furthermore, we theorize that effects of personality-relationship transactions on health also vary with the normativeness of the eliciting life transition. © 2013 Wiley Periodicals, Inc.

  12. Leukemia and ionizing radiation revisited

    Energy Technology Data Exchange (ETDEWEB)

    Cuttler, J.M. [Cuttler & Associates Inc., Vaughan, Ontario (Canada); Welsh, J.S. [Loyola University-Chicago, Dept. or Radiation Oncology, Stritch School of Medicine, Maywood, Illinois (United States)

    2016-03-15

    A world-wide radiation health scare was created in the late 19508 to stop the testing of atomic bombs and block the development of nuclear energy. In spite of the large amount of evidence that contradicts the cancer predictions, this fear continues. It impairs the use of low radiation doses in medical diagnostic imaging and radiation therapy. This brief article revisits the second of two key studies, which revolutionized radiation protection, and identifies a serious error that was missed. This error in analyzing the leukemia incidence among the 195,000 survivors, in the combined exposed populations of Hiroshima and Nagasaki, invalidates use of the LNT model for assessing the risk of cancer from ionizing radiation. The threshold acute dose for radiation-induced leukemia, based on about 96,800 humans, is identified to be about 50 rem, or 0.5 Sv. It is reasonable to expect that the thresholds for other cancer types are higher than this level. No predictions or hints of excess cancer risk (or any other health risk) should be made for an acute exposure below this value until there is scientific evidence to support the LNT hypothesis. (author)

  13. Individualist Biocentrism vs. Holism Revisited

    Directory of Open Access Journals (Sweden)

    Katie McShane

    2014-06-01

    Full Text Available While holist views such as ecocentrism have considerable intuitive appeal, arguing for the moral considerability of ecological wholes such as ecosystems has turned out to be a very difficult task. In the environmental ethics literature, individualist biocentrists have persuasively argued that individual organisms—but not ecological wholes—are properly regarded as having a good of their own . In this paper, I revisit those arguments and contend that they are fatally flawed. The paper proceeds in five parts. First, I consider some problems brought about by climate change for environmental conservation strategies and argue that these problems give us good pragmatic reasons to want a better account of the welfare of ecological wholes. Second, I describe the theoretical assumptions from normative ethics that form the background of the arguments against holism. Third, I review the arguments given by individualist biocentrists in favour of individualism over holism. Fourth, I review recent work in the philosophy of biology on the units of selection problem, work in medicine on the human biome, and work in evolutionary biology on epigenetics and endogenous viral elements. I show how these developments undermine both the individualist arguments described above as well as the distinction between individuals and wholes as it has been understood by individualists. Finally, I consider five possible theoretical responses to these problems.

  14. The mycorrhiza helper bacteria revisited.

    Science.gov (United States)

    Frey-Klett, P; Garbaye, J; Tarkka, M

    2007-01-01

    In natural conditions, mycorrhizal fungi are surrounded by complex microbial communities, which modulate the mycorrhizal symbiosis. Here, the focus is on the so-called mycorrhiza helper bacteria (MHB). This concept is revisited, and the distinction is made between the helper bacteria, which assist mycorrhiza formation, and those that interact positively with the functioning of the symbiosis. After considering some examples of MHB from the literature, the ecological and evolutionary implications of the relationships of MHB with mycorrhizal fungi are discussed. The question of the specificity of the MHB effect is addressed, and an assessment is made of progress in understanding the mechanisms of the MHB effect, which has been made possible through the development of genomics. Finally, clear evidence is presented suggesting that some MHB promote the functioning of the mycorrhizal symbiosis. This is illustrated for three critical functions of practical significance: nutrient mobilization from soil minerals, fixation of atmospheric nitrogen, and protection of plants against root pathogens. The review concludes with discussion of future research priorities regarding the potentially very fruitful concept of MHB.

  15. Vitreous substitutes: challenges and directions.

    Science.gov (United States)

    Gao, Qian-Ying; Fu, Yue; Hui, Yan-Nian

    2015-01-01

    The natural vitreous body has a fine structure and complex functions. The imitation of the natural vitreous body by vitreous substitutes is a challenging work for both researchers and ophthalmologists. Gases, silicone oil, heavy silicone oil and hydrogels, particularly the former two vitreous substitutes are clinically widely used with certain complications. Those, however, are not real artificial vitreous due to lack of structure and function like the natural vitreous body. This article reviews the situations, challenges, and future directions in the development of vitreous substitutes, particularly the experimental and clinical use of a new artificial foldable capsular vitreous body.

  16. The Future of Engineering Education--Revisited

    Science.gov (United States)

    Wankat, Phillip C.; Bullard, Lisa G.

    2016-01-01

    This paper revisits the landmark CEE series, "The Future of Engineering Education," published in 2000 (available free in the CEE archives on the internet) to examine the predictions made in the original paper as well as the tools and approaches documented. Most of the advice offered in the original series remains current. Despite new…

  17. Revisiting separation properties of convex fuzzy sets

    Science.gov (United States)

    Separation of convex sets by hyperplanes has been extensively studied on crisp sets. In a seminal paper separability and convexity are investigated, however there is a flaw on the definition of degree of separation. We revisited separation on convex fuzzy sets that have level-wise (crisp) disjointne...

  18. The Evil of Banality: Arendt Revisited

    Science.gov (United States)

    Minnich, Elizabeth

    2014-01-01

    "The banality of evil" (Arendt) remains controversial and useful. Ironically, the concept is now itself a banality. To revisit and extend it, we consider the "evil of banality", the profound dangers of cliched thoughtlessness. A distinction is proposed: "intensive" versus "extensive evils". The former takes…

  19. Natural Language Processing concepts and methods revisited

    OpenAIRE

    IJSMI,EDITOR

    2017-01-01

    The paper starts with the history of Natural Language Processing (NLP) and revisits the concepts and methods involved in the NLP. It provides overview of different classifiers and language modelling techniques. The paper also lists the different fields where NLP is used and also the software available to carry out NLP.

  20. The methodology of corpus cavernosum electromyography revisited

    NARCIS (Netherlands)

    Jiang, X. G.; Wijkstra, H.; Meuleman, E. J. H.; Wagner, G.

    2004-01-01

    Objective: The methodology of corpus cavernosum electromyography (CC-EMG) was revisited, in order to overcome current methodological difficulties that hinder its clinical application. Materials and methods: Using an 8-channel device, CC-EMG was performed in 12 healthy volunteers. Surface electrodes

  1. Spectral Quasi-Equilibrium Manifold for Chemical Kinetics.

    Science.gov (United States)

    Kooshkbaghi, Mahdi; Frouzakis, Christos E; Boulouchos, Konstantinos; Karlin, Iliya V

    2016-05-26

    The Spectral Quasi-Equilibrium Manifold (SQEM) method is a model reduction technique for chemical kinetics based on entropy maximization under constraints built by the slowest eigenvectors at equilibrium. The method is revisited here and discussed and validated through the Michaelis-Menten kinetic scheme, and the quality of the reduction is related to the temporal evolution and the gap between eigenvalues. SQEM is then applied to detailed reaction mechanisms for the homogeneous combustion of hydrogen, syngas, and methane mixtures with air in adiabatic constant pressure reactors. The system states computed using SQEM are compared with those obtained by direct integration of the detailed mechanism, and good agreement between the reduced and the detailed descriptions is demonstrated. The SQEM reduced model of hydrogen/air combustion is also compared with another similar technique, the Rate-Controlled Constrained-Equilibrium (RCCE). For the same number of representative variables, SQEM is found to provide a more accurate description.

  2. Dyscravia: voicing substitution dysgraphia.

    Science.gov (United States)

    Gvion, Aviah; Friedmann, Naama

    2010-06-01

    We report a new type of dysgraphia, which we term dyscravia. The main error type in dyscravia is substitution of the target letter with a letter that differs only with respect to the voicing feature, such as writing "coat" for "goat", and "vagd" for "fact". Two Hebrew-speaking individuals with acquired dyscravia are reported, TG, a man aged 31, and BG, a woman aged 66. Both had surface dysgraphia in addition to their dyscravia. To describe dyscravia in detail, and to explore the rate and types of errors made in spelling, we administered tests of writing to dictation, written naming, and oral spelling. In writing to dictation, TG made voicing errors on 38% of the words, and BG made 17% voicing errors. Voicing errors also occurred in nonword writing (43% for TG, 56% for BG). The writing performance and the variables that influenced the participants' spelling, as well as the results of the auditory discrimination and repetition tasks indicated that their dyscravia did not result from a deficit in auditory processing, the graphemic buffer, the phonological output lexicon, the phonological output buffer, or the allographic stage. The locus of the deficit is the phoneme-to-grapheme conversion, in a function specialized in the conversion of phonemes' voicing feature into graphemes. Because these participants had surface dysgraphia and were forced to write via the sublexical route, the deficit in voicing was evident in their writing of both words and nonwords. We further examined whether the participants also evinced parallel errors in reading. TG had a selective voicing deficit in writing, and did not show any voicing errors in reading, whereas BG had voicing errors also in the reading of nonwords (i.e., she had dyslegzia in addition to dyscravia). The dissociation TG demonstrated indicated that the voicing feature conversion is separate for reading and writing, and can be impaired selectively in writing. BG's dyslegzia indicates that the grapheme-to-phoneme conversion

  3. Commercial formalin substitutes for histopathology

    DEFF Research Database (Denmark)

    Prentø, P; Lyon, H

    1997-01-01

    We compared the performance of six commercial fixatives proposed to be formalin substitutes with the performance of buffered formalin, Clarke's ethanol-acetic acid, and ethanol, using rat liver, small intestine, and kidney. We investigated the rate of penetration, mode of fixation, extent of prot...... was obtained by combining formalin fixation with antigen retrieval. We conclude that none of the proposed commercial substitutes for buffered formalin are adequate for critical histology or histopathology....

  4. Ambulatory thyroidectomy: a multistate study of revisits and complications.

    Science.gov (United States)

    Orosco, Ryan K; Lin, Harrison W; Bhattacharyya, Neil

    2015-06-01

    Determine rates and reasons for revisits after ambulatory adult thyroidectomy. Cross-sectional analysis of multistate ambulatory surgery and hospital databases. Ambulatory surgery data from the State Ambulatory Surgery Databases of California, Florida, Iowa, and New York for calendar years 2010 and 2011. Ambulatory thyroidectomy cases were linked to state ambulatory, emergency, and inpatient databases for revisit encounters occurring within 30 days. The numbers of revisits, mortality, and associated diagnoses were analyzed. A total of 25,634 cases of ambulatory thyroid surgery were identified: 44.2% total thyroidectomy (TT) and 55.8% partial thyroidectomy (PT). Common indications for surgery included goiter/cyst (39.5%), benign/uncertain neoplasm (24.2%), and malignant neoplasm (24.0%). The 30-day revisit rate was 7.2% (n = 1858; 61.8% emergency department, 22.4% inpatient admission, and 15.8% ambulatory surgery center). The most common diagnosis at revisit was hypocalcemia (20.8% of revisits), followed by wound hematoma/seroma/bleeding (7.1%). Higher rates of revisit, hypocalcemia, and hematoma/seroma/bleeding were seen in patients undergoing TT (P ambulatory thyroidectomy demonstrates a good postoperative morbidity and mortality profile. Common reasons for revisits included hypocalcemia and bleeding/seroma/hematoma, which occurred with relatively high frequencies as late as a week after surgery. Quality improvement measures should be targeted at lowering revisit rates and safely managing complications. © American Academy of Otolaryngology—Head and Neck Surgery Foundation 2015.

  5. The interaction of atoms with LiF(001) revisited

    CERN Document Server

    Miraglia, J E

    2016-01-01

    Pairwise additive potentials for multielectronic atoms interacting with a LiF(001) surface are revisited by including an improved description of the electron density associated with the different lattice sites, as well as non-local electron density contributions. Within this model, the electron distribution around each ionic site of the crystal is described by means of an onion approach that accounts for the influence of the Madelung potential. From such densities, binary interatomic potentials are then derived by using well-known non-local functionals for the kinetic, exchange and correlation terms. Rumpling and long-range contributions due to projectile polarization and van der Waals forces are also included in an analogous fashion. We apply this pairwise additive approximation to evaluate the interaction potential between closed-shell - He, Ne, Ar, Kr, and Xe - and open-shell - N, S, and Cl - atoms and the LiF surface, analyzing the relative importance of the different contributions. The performance of the...

  6. Revisiting the 1761 Transatlantic Tsunami

    Science.gov (United States)

    Baptista, Maria Ana; Wronna, Martin; Miranda, Jorge Miguel

    2016-04-01

    The tsunami catalogs of the Atlantic include two transatlantic tsunamis in the 18th century the well known 1st November 1755 and the 31st March 1761. The 31st March 1761 earthquake struck Portugal, Spain, and Morocco. The earthquake occurred around noontime in Lisbon alarming the inhabitants and throwing down ruins of the past 1st November 1755 earthquake. According to several sources, the earthquake was followed by a tsunami observed as far as Cornwall (United Kingdom), Cork (Ireland) and Barbados (Caribbean). The analysis of macroseismic information and its compatibility with tsunami travel time information led to a source area close to the Ampere Seamount with an estimated epicenter circa 34.5°N 13°W. The estimated magnitude of the earthquake was 8.5. In this study, we revisit the tsunami observations, and we include a report from Cadiz not used before. We use the results of the compilation of the multi-beam bathymetric data, that covers the area between 34°N - 38°N and 12.5°W - 5.5°W and use the recent tectonic map published for the Southwest Iberian Margin to select among possible source scenarios. Finally, we use a non-linear shallow water model that includes the discretization and explicit leap-frog finite difference scheme to solve the shallow water equations in the spherical or Cartesian coordinate to compute tsunami waveforms and tsunami inundation and check the results against the historical descriptions to infer the source of the event. This study received funding from project ASTARTE- Assessment Strategy and Risk Reduction for Tsunamis in Europe a collaborative project Grant 603839, FP7-ENV2013 6.4-3

  7. Dynamics of competitive reactions: endothermic proton transfer and exothermic substitution.

    Science.gov (United States)

    Ren, Jianhua; Brauman, John I

    2004-03-03

    Dynamics of an endothermic proton-transfer reaction, F(-) with dimethyl sulfoxide, and an endothermic proton-transfer reaction with a competing exothermic substitution (S(N)2) channel, F(-) with borane-methyl sulfide complex, were investigated using a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR) and kinetic modeling. The two proton-transfer reactions have slightly positive and a small negative overall free energy changes, respectively. Energy-dependent rate constants were measured as a function of F(-) ion translational energy, and the resulting kinetics were modeled with the RRKM (Rice-Ramsperger-Kassel-Marcus) theory. The observed rate constants for the proton-transfer reactions of F(-) with dimethyl sulfoxide and with borane-methyl sulfide complex are identical, with a value of 0.17 x 10(-9) cm(3) molecule(-1) s(-1); for the S(N)2 reaction, k = 0.90 x 10(-9) cm(3) molecule(-1) s(-1) at 350 K. Both proton-transfer reactions have positive entropy changes in the forward direction and show positive energy dependences. The competing S(N)2 reaction exhibits negative energy dependence and becomes less important at higher energies. The changes of the observed rate constants agree with RRKM theory predictions for a few kcal/mol of additional kinetic energy. The dynamic change of the branching ratio for the competing proton transfer and the substitution reactions results from the competition between the microscopic rate constants associated with each channel.

  8. Extrinsic doping in silicon revisited

    KAUST Repository

    Schwingenschlögl, Udo

    2010-06-17

    Both n-type and p-type doping of silicon is at odds with the charge transfer predicted by Pauling electronegativities and can only be reconciled if we no longer regarding dopant species as isolated atoms but rather consider them as clusters consisting of the dopant and its four nearest neighbor silicon atoms. The process that gives rise to n-type and p-type effects is the charge redistribution that occurs between the dopant and its neighbors, as we illustrate here using electronic structure calculations. This view point is able to explain why conventional substitutional n-type doping of carbon has been so difficult.

  9. Parkinson disease and smoking revisited

    DEFF Research Database (Denmark)

    Ritz, Beate; Lee, Pei-Chen; Lassen, Christina F

    2014-01-01

    OBJECTIVE: To assess whether being able to quit smoking is an early marker of Parkinson disease (PD) onset rather than tobacco being "neuroprotective," we analyzed information about ease of quitting and nicotine substitute use. METHODS: For this case-control study, we identified 1,808 patients wi......, or constipation and suggests that the apparent "neuroprotective" effect of smoking observed in epidemiologic studies is due to reverse causation....... with PD diagnosed between 1996 and 2009 from Danish registries, matched 1,876 population controls on sex and year of birth, and collected lifestyle information. We estimated odds ratios and 95% confidence intervals with logistic regression adjusting for matching factors and confounders. RESULTS: Fewer...

  10. Sterically Hindered Square-Planar Nickel(II) Organometallic Complexes: Preparation, Characterization, and Substitution Behavior

    Science.gov (United States)

    Martinez, Manuel; Muller, Guillermo; Rocamora, Merce; Rodriguez, Carlos

    2007-01-01

    The series of experiments proposed for advanced undergraduate students deal with both standard organometallic preparative methods in dry anaerobic conditions and with a kinetic study of the mechanisms operating in the substitution of square-planar complexes. The preparation of organometallic compounds is carried out by transmetallation or…

  11. Effect of electron-withdrawing power of the substituted group on OH ...

    Indian Academy of Sciences (India)

    Effect of electron-withdrawing power of the substituted group on ... depending on the concentration of acid and electron-withdrawing power, solute .... reaction of. •. OH radical with PTA was determined by formation kinetic studies at 330 and. 360 nm. The pseudo-first order rate increased linearly with solute concentration and ...

  12. Approaches in Substitution of Organic Solvents

    DEFF Research Database (Denmark)

    Jacobsen, Thomas

    2000-01-01

    In substitution of harmful chemicals or products with less harmful or harmless ones, there are different approaches according to the different situations, the technical requirements to the substitutes, and the goals for the substitution. Three different cases are presented. The substitution proce...

  13. Fish species substitution and misnaming in South Africa: An economic, safety and sustainability conundrum revisited.

    Science.gov (United States)

    Cawthorn, Donna-Mareè; Duncan, John; Kastern, Chris; Francis, Junaid; Hoffman, Louwrens C

    2015-10-15

    While fish species mislabelling has emerged as a global problem, the tracking of improvements or deteriorations in seafood trading practices is challenging without a consistent basis for monitoring. The aim of this study was to develop a robust, repeatable species authentication protocol that could be used to benchmark the current and future incidences of fish mislabelling in South Africa. Using this approach, 149 fish samples collected from restaurants and retailers in three provinces (KwaZulu-Natal, Western Cape and Gauteng) were identified using DNA barcoding, supplemented in certain cases with mitochondrial control region sequencing. Overall, 18% of samples were incorrectly described in terms of species, with similar misrepresentation rates in restaurants (18%) and retail outlets (19%). While there appears to be some improvement in the transparency of local seafood marketing compared to previous studies, the results remain of concern and signal the need for enhanced seafood labelling regulations, monitoring and law enforcement. Copyright © 2015 Elsevier Ltd. All rights reserved.

  14. 40 CFR 721.10040 - Substituted acridine naphtha substituted benzamide (generic).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted acridine naphtha... Significant New Uses for Specific Chemical Substances § 721.10040 Substituted acridine naphtha substituted... substance identified generically as a substituted acridine naphtha substituted benzamide (PMN P-02-522) is...

  15. Revisiting Cementoblastoma with a Rare Case Presentation

    Directory of Open Access Journals (Sweden)

    Vijayanirmala Subramani

    2017-01-01

    Full Text Available Cementoblastoma is a rare benign odontogenic neoplasm which is characterized by the proliferation of cellular cementum. Diagnosis of cementoblastoma is challenging because of its protracted clinical, radiographic features, and bland histological appearance; most often cementoblastoma is often confused with other cementum and bone originated lesions. The aim of this article is to overview/revisit, approach the diagnosis of cementoblastoma, and also present a unique radiographic appearance of a cementoblastoma lesion associated with an impacted tooth.

  16. The Faraday effect revisited: General theory

    OpenAIRE

    Cornean, Horia Decebal; Nenciu, Gheorghe; Pedersen, Thomas Garm

    2005-01-01

    This paper is the first in a series revisiting the Faraday effect, or more generally, the theory of electronic quantum transport/optical response in bulk media in the presence of a constant magnetic field. The independent electron approximation is assumed. For free electrons, the transverse conductivity can be explicitly computed and coincides with the classical result. In the general case, using magnetic perturbation theory, the conductivity tensor is expanded in powers of the strength of th...

  17. Substitution determination of Fmoc‐substituted resins at different wavelengths

    Science.gov (United States)

    Kley, Markus; Bächle, Dirk; Loidl, Günther; Meier, Thomas; Samson, Daniel

    2017-01-01

    In solid‐phase peptide synthesis, the nominal batch size is calculated using the starting resin substitution and the mass of the starting resin. The starting resin substitution constitutes the basis for the calculation of a whole set of important process parameters, such as the number of amino acid derivative equivalents. For Fmoc‐substituted resins, substitution determination is often performed by suspending the Fmoc‐protected starting resin in 20% (v/v) piperidine in DMF to generate the dibenzofulvene–piperidine adduct that is quantified by ultraviolet–visible spectroscopy. The spectrometric measurement is performed at the maximum absorption wavelength of the dibenzofulvene–piperidine adduct, that is, at 301.0 nm. The recorded absorption value, the resin weight and the volume are entered into an equation derived from Lambert–Beer's law, together with the substance‐specific molar absorption coefficient at 301.0 nm, in order to calculate the nominal substitution. To our knowledge, molar absorption coefficients between 7100 l mol−1 cm−1 and 8100 l mol−1 cm−1 have been reported for the dibenzofulvene–piperidine adduct at 301.0 nm. Depending on the applied value, the nominal batch size may differ up to 14%. In this publication, a determination of the molar absorption coefficients at 301.0 and 289.8 nm is reported. Furthermore, proof is given that by measuring the absorption at 289.8 nm the impact of wavelength accuracy is reduced. © 2017 The Authors Journal of Peptide Science published by European Peptide Society and John Wiley & Sons Ltd. PMID:28635051

  18. Smart Phones and their Substitutes

    DEFF Research Database (Denmark)

    Bødker, Mads; Gimpel, Gregory; Hedman, Jonas

    2009-01-01

    our understanding of the role of substitutes, device content fit issues, and implications for business models by asking the question: What is an effective business model to address the relationship between user preference and the fit of the smart phone and everyday task? The field study data suggest...

  19. Sensory Substitution for Wounded Servicemembers

    Science.gov (United States)

    2009-10-28

    Rehabilitation The IHMC Mobility Assist Exoskeleton (Figure 12) has great potential for gait rehabilitation because of its high fidelity impedance control...mobility assist exoskeleton technologies. Through sensory substitution device demonstrations, we solicited subjective situation awareness feedback...with TBI also evaluated the passive mobility assist exoskeleton , which enabled him to walk at a normal gait, unassisted, for the first time since

  20. ORIGINAL ARTICLES Mandatory substitution successful

    African Journals Online (AJOL)

    Yet private health care is the dominant vehicle for both the financing and provision of health care in the country.1 Generic substitution in this sector, therefore, has the potential to cut medication costs significantly. The Medicines and Related Substances Control Amendment. Act No. 90 of 1997 (hereinafter referred to as 'The ...

  1. No Substitute Teacher Left behind

    Science.gov (United States)

    O'Connor, Kevin

    2009-01-01

    Schools and districts routinely recruit, retain, and support highly qualified teachers to ensure that students receive the best learning opportunities. However, even if one's school employs highly qualified full-time teachers, it is important to acknowledge that substitute teachers also have a significant impact on the education of students. One…

  2. Efficient synthesis of substituted dihydrotetraazapentacenes.

    Science.gov (United States)

    Seillan, Claire; Brisset, Hugues; Siri, Olivier

    2008-09-18

    We describe a versatile and very efficient synthesis of previously unknown substituted 5,14-dihydro-5,7,12,14-tetraazapentacenes (DHTAPs). A structural study by NMR spectroscopy showed that the conjugated pi-system of the pentacyclic skeleton rearranges depending on the electronic effect of the substituent(s).

  3. Tax rates as strategic substitutes

    NARCIS (Netherlands)

    H. Vrijburg (Hendrik); R.A. de Mooij (Ruud)

    2016-01-01

    textabstractThis paper analytically derives conditions under which the slope of the tax-reaction function is negative in a classical tax competition model. If countries maximize welfare, a negative slope (reflecting strategic substitutability) occurs under relatively mild conditions. The strategic

  4. Potential for structural lumber substitutes

    Science.gov (United States)

    Theodore L. Laufenberg

    1985-01-01

    The potential for substitution of structural wood composites into solid-sawn lumber markets is presented from the technological viewpoint. Technological limitations of existing composite processes and products are reviewed in the context of the present laminated veneer lumber (LVL), flakeboard, and fiber/ paper industries. The limits of mechanical property potential...

  5. Automatic extraction of ingredient's substitutes

    NARCIS (Netherlands)

    Boscarino, C.; Koenderink, N.J.J.P.; Nedovic, V; Top, J.L.

    2014-01-01

    Expert advice on how ingredients can be replaced in recipes is widely available on-line. However, these are general substitution rules, which do not take into account contextual factors such as culture, sensory perception, season, etc. We aim at tuning general rules to particular recipes. From an

  6. Biopharmaceutic classification of drugs revisited.

    Science.gov (United States)

    Daousani, Chrysa; Macheras, Panos

    2016-12-01

    The biopharmaceutics classification system (BCS) was based on the tube model of the intestinal lumen. This model considers constant drug permeability along the intestines, a plug flow fluid with the suspended drug particles moving with the fluid, and dissolution in the small particle limit. Since then the research work focusing on drug gastrointestinal (GI) absorption phenomena and processes rely on the classical laws of transport, diffusion and kinetics; however, the homogeneous assumptions associated with the well-stirred Euclidean media, where the classical laws of diffusion and kinetics apply, have been questioned in the past. In this work we explore the biopharmaceutic classification of drugs using a heterogeneous pseudo steady-state model of oral drug absorption. The fraction of dose absorbed (Fabs) was expressed as a function of two time-dependent processes where time dependent coefficients govern drug absorption and non-absorption processes. Fundamental drug properties like the absorption potential are correlated with Fabs and allow the biopharmaceutic classification of drugs taking into account the heterogeneous aspects of oral drug absorption. This analysis reveals that for Class I drugs no time dependency is expected for both absorption and non absorption processes since the gastric emptying is controlling the absorption of Class I drugs while the completion of absorption (Fabs>90%) is terminated along the first part of the jejunum. Due to the biopharmaceutical properties of Class II, III and IV drugs, these drugs travel throughout the GI tract and therefore both absorption and non absorption processes will exhibit time dependency. Thus, the calculation of Fabs (<90%) for Class II, III and IV is dependent on the estimates of the time exponents of time dependent coefficients controlling drug absorption e.g. dissolution, uptake or non absorption e.g. precipitation. Copyright © 2016 Elsevier B.V. All rights reserved.

  7. Biochemical reactions in crowded environments: Revisiting the effects of volume exclusion with simulations

    Directory of Open Access Journals (Sweden)

    David eGomez

    2015-06-01

    Full Text Available Molecular crowding is ubiquitous within cells and affects many biological processes including protein-protein binding, enzyme activities and gene regulation. Here we revisit some generic effects of crowding using a combination of lattice simulations and reaction-diffusion simulations with the program ReaDDy. Specifically, we implement three reactions, simple binding, a diffusion-limited reaction and a reaction with Michaelis-Menten kinetics. Histograms of binding and unbinding times provide a detailed picture how crowding affects these reactions and how the separate effects of crowding on binding equilibrium and on diffusion act together. In addition, we discuss how crowding affects processes related to gene expression such as RNA polymerase-promoter binding and translation elongation.

  8. 40 CFR 721.981 - Substituted naphtholoazo-substituted naphthalenyl-substituted azonaphthol chromium complex.

    Science.gov (United States)

    2010-07-01

    ... ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL... uses subject to reporting. (1) The chemical substance identified generically as a substituted... subpart A of this part apply to this section except as modified by this paragraph. (1) Recordkeeping...

  9. Principles of chemical kinetics

    CERN Document Server

    House, James E

    2007-01-01

    James House's revised Principles of Chemical Kinetics provides a clear and logical description of chemical kinetics in a manner unlike any other book of its kind. Clearly written with detailed derivations, the text allows students to move rapidly from theoretical concepts of rates of reaction to concrete applications. Unlike other texts, House presents a balanced treatment of kinetic reactions in gas, solution, and solid states. The entire text has been revised and includes many new sections and an additional chapter on applications of kinetics. The topics covered include quantitative rela

  10. Introduction to chemical kinetics

    CERN Document Server

    Soustelle, Michel

    2013-01-01

    This book is a progressive presentation of kinetics of the chemical reactions. It provides complete coverage of the domain of chemical kinetics, which is necessary for the various future users in the fields of Chemistry, Physical Chemistry, Materials Science, Chemical Engineering, Macromolecular Chemistry and Combustion. It will help them to understand the most sophisticated knowledge of their future job area. Over 15 chapters, this book present the fundamentals of chemical kinetics, its relations with reaction mechanisms and kinetic properties. Two chapters are then devoted to experimental re

  11. Measuring hospital quality using pediatric readmission and revisit rates.

    Science.gov (United States)

    Bardach, Naomi S; Vittinghoff, Eric; Asteria-Peñaloza, Renée; Edwards, Jeffrey D; Yazdany, Jinoos; Lee, Henry C; Boscardin, W John; Cabana, Michael D; Dudley, R Adams

    2013-09-01

    To assess variation among hospitals on pediatric readmission and revisit rates and to determine the number of high- and low-performing hospitals. In a retrospective analysis using the State Inpatient and Emergency Department Databases from the Healthcare Cost and Utilization Project with revisit linkages available, we identified pediatric (ages 1-20 years) visits with 1 of 7 common inpatient pediatric conditions (asthma, dehydration, pneumonia, appendicitis, skin infections, mood disorders, and epilepsy). For each condition, we calculated rates of all-cause readmissions and rates of revisits (readmission or presentation to the emergency department) within 30 and 60 days of discharge. We used mixed logistic models to estimate hospital-level risk-standardized 30-day revisit rates and to identify hospitals that had performance statistically different from the group mean. Thirty-day readmission rates were low (1% of hospitals labeled as different from the mean on 30-day risk-standardized revisit rates was mood disorders (4.2% of hospitals [n = 15], range of hospital performance 6.3%-15.9%). We found that when comparing hospitals' performances to the average, few hospitals that care for children are identified as high- or low-performers for revisits, even for common pediatric diagnoses, likely due to low hospital volumes. This limits the usefulness of condition-specific readmission or revisit measures in pediatric quality measurement.

  12. Currency Substitution and Financial Innovation.

    OpenAIRE

    Pablo E. Guidotti

    1993-01-01

    This paper explores the domestic effects as well as the international transmission of financial innovation. The analysis is carried out in a cash-in-advance model with two currencies and tw o goods in which income velocity is variable because of inventory-type considerations in the determination of the demand for money. The discussion emphasizes the role of currency substitution, which occur s through the interaction between the two monies in affecting the tota l amount of time devoted to tra...

  13. (nitro substituted-phenyl)-hydrazonomethyl

    Indian Academy of Sciences (India)

    5c. Et. CH3 NO2. NO2. 5d. Me H. NO2. NO2. 5e. Et. Br. H. NO2. Scheme 1. Synthesis of receptors 5a–5e. Reagents and conditions: (i) TFA, H2O, room temperature, 15 min;. (ii) DMF-POCl3, 0. ◦. C, 2.5–3 h; (iii) substituted phenyl hydrazine derivative, ethanol, reflux, 1–2 h. The anion binding characteristics of receptors 5a– ...

  14. Substituted Indoleacetic Acids Tested in Tissue Cultures

    DEFF Research Database (Denmark)

    Engvild, Kjeld Christensen

    1978-01-01

    Monochloro substituted IAA inhibited shoot induction in tobacco tissue cultures about as much as IAA. Dichloro substituted IAA inhibited shoot formation less. Other substituted IAA except 5-fluoro- and 5-bromoindole-3-acetic acid were less active than IAA. Callus growth was quite variable...

  15. 24 CFR 234.256 - Substitute mortgagors.

    Science.gov (United States)

    2010-04-01

    ... 24 Housing and Urban Development 2 2010-04-01 2010-04-01 false Substitute mortgagors. 234.256... Substitute mortgagors. (a) Selling mortgagor. The requirements for the selling mortgagor are set forth in... Commissioner's approval of a substitute mortgagor only if the mortgage executed by the original mortgagor met...

  16. 21 CFR 882.5910 - Dura substitute.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Dura substitute. 882.5910 Section 882.5910 Food... DEVICES NEUROLOGICAL DEVICES Neurological Therapeutic Devices § 882.5910 Dura substitute. (a) Identification. A dura substitute is a sheet or material that is used to repair the dura mater (the membrane...

  17. 24 CFR 235.206 - Substitute mortgagors.

    Science.gov (United States)

    2010-04-01

    ... 24 Housing and Urban Development 2 2010-04-01 2010-04-01 false Substitute mortgagors. 235.206... and Obligations-Homes for Lower Income Families § 235.206 Substitute mortgagors. (a) Selling mortgagor... if it obtains the Commissioner's approval of a substitute mortgagor, as provided under this section...

  18. 37 CFR 1.125 - Substitute specification.

    Science.gov (United States)

    2010-07-01

    ... 37 Patents, Trademarks, and Copyrights 1 2010-07-01 2010-07-01 false Substitute specification. 1... § 1.125 Substitute specification. (a) If the number or nature of the amendments or the legibility of... thereof, be rewritten. (b) Subject to § 1.312, a substitute specification, excluding the claims, may be...

  19. 24 CFR 203.258 - Substitute mortgagors.

    Science.gov (United States)

    2010-04-01

    ... 24 Housing and Urban Development 2 2010-04-01 2010-04-01 false Substitute mortgagors. 203.258... § 203.258 Substitute mortgagors. (a) Selling mortgagor. Except as provided in paragraph (d) of this..., only if it obtains the Commissioner's approval of a substitute mortgagor, as provided by this section...

  20. 24 CFR 220.253 - Substitute mortgagors.

    Science.gov (United States)

    2010-04-01

    ... 24 Housing and Urban Development 2 2010-04-01 2010-04-01 false Substitute mortgagors. 220.253... Contract Rights and Obligations-Homes § 220.253 Substitute mortgagors. (a) Selling mortgagor. The mortgagee... the Commissioner's approval of a substitute mortgagor, as provided by this section. (b) Purchasing...

  1. 24 CFR 221.252 - Substitute mortgagors.

    Science.gov (United States)

    2010-04-01

    ... 24 Housing and Urban Development 2 2010-04-01 2010-04-01 false Substitute mortgagors. 221.252... Cost Homes § 221.252 Substitute mortgagors. (a) Selling mortgagor. The mortgagee may effect the release... approval of a substitute mortgagor, as provided by this section. (b) Purchasing mortgagor. The Commissioner...

  2. 40 CFR 192.42 - Substitute provisions.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 24 2010-07-01 2010-07-01 false Substitute provisions. 192.42 Section 192.42 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) RADIATION PROTECTION... § 192.42 Substitute provisions. The regulatory agency may, with the concurrence of EPA, substitute for...

  3. 40 CFR 721.323 - Substituted acrylamide.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted acrylamide. 721.323... Substances § 721.323 Substituted acrylamide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance generically identified as substituted acrylamide (PMN P-90-1687) is...

  4. Sloan Digital Sky Survey Photometric Calibration Revisited

    Energy Technology Data Exchange (ETDEWEB)

    Marriner, John; /Fermilab

    2012-06-29

    The Sloan Digital Sky Survey calibration is revisited to obtain the most accurate photometric calibration. A small but significant error is found in the flat-fielding of the Photometric telescope used for calibration. Two SDSS star catalogs are compared and the average difference in magnitude as a function of right ascension and declination exhibits small systematic errors in relative calibration. The photometric transformation from the SDSS Photometric Telescope to the 2.5 m telescope is recomputed and compared to synthetic magnitudes computed from measured filter bandpasses.

  5. Ozone measurements with meteors: a revisit

    Science.gov (United States)

    Ye, Quan-Zhi; Han, Summer Xia

    2017-11-01

    Understanding the role of ozone in the mesosphere/lower thermosphere (MLT) region is essential for understanding the atmospheric processes in the upper atmosphere. Earlier studies have shown that it is possible to use overdense meteor trails to measure ozone concentration in the meteor region. Here, we revisit this topic by comparing a compilation of radar observations to satellite measurements. We observe a modest agreement between the values derived from these two methods, which confirm the usefulness of the meteor trail technique for measuring ozone content at certain heights in the MLT region. Future simultaneous measurements will help quantifying the performance of this technique.

  6. Large J expansion in ABJM theory revisited.

    Science.gov (United States)

    Dimov, H; Mladenov, S; Rashkov, R C

    Recently there has been progress in the computation of the anomalous dimensions of gauge theory operators at strong coupling by making use of the AdS/CFT correspondence. On the string theory side they are given by dispersion relations in the semiclassical regime. We revisit the problem of a large-charge expansion of the dispersion relations for simple semiclassical strings in an [Formula: see text] background. We present the calculation of the corresponding anomalous dimensions of the gauge theory operators to an arbitrary order using three different methods. Although the results of the three methods look different, power series expansions show their consistency.

  7. Revisiting the texture zero neutrino mass matrices

    Science.gov (United States)

    Singh, Madan; Ahuja, Gulsheen; Gupta, Manmohan

    2016-12-01

    In the light of refined and large measurements of the reactor mixing angle θ, we have revisited the texture three- and two-zero neutrino mass matrices in the flavor basis. For Majorana neutrinos, it has been explicitly shown that all the texture three-zero mass matrices remain ruled out. Further, for both normal and inverted mass ordering, for the texture two-zero neutrino mass matrices one finds interesting constraints on the Dirac-like CP-violating phase δ and Majorana phases ρ and σ.

  8. 40 CFR 721.6920 - Butyl acrylate, polymer with substituted methyl styrene, methyl methacrylate, and substituted...

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Butyl acrylate, polymer with... acrylate, polymer with substituted methyl styrene, methyl methacrylate, and substituted silane. (a... butyl acrylate, polymer with substituted methyl styrene, methyl methacrylate, and substituted silane...

  9. Working School Children in a Nigerian Community: Revisiting the ...

    African Journals Online (AJOL)

    Working School Children in a Nigerian Community: Revisiting the Issues. ... work on school performance and health consequences of child labour among school children in a rapidly ... The academic records of the students were also reviewed.

  10. Containment Revisited: An Old Approach to Future Challenges

    National Research Council Canada - National Science Library

    Lindamood, Brian

    2002-01-01

    .... The global nature of the new world order provides a grand setting for a revisit to Kennan's thoughts, giving America an unprecedented opportunity to secure itself and her allies without the 'rapid...

  11. Ground Zero revisits shape outbreaks: Zika and beyond

    CERN Document Server

    Manrique, Pedro D; Johnson, Neil F

    2016-01-01

    During an infection outbreak, many people continue to revisit Ground Zero - such as the one square mile of Miami involved in the current Zika outbreak- for work, family or social reasons. Public health planning must account for the counterintuitive ways in which this human flow affects the outbreak's duration, severity and time-to-peak. Managing this flow of revisits can allow the outbreak's evolution to be tailored.

  12. Kanter revisited: Gender, power and (in)visibility

    OpenAIRE

    Lewis, P.; Simpson, R

    2012-01-01

    This is the accepted version of the following article: Lewis, P. and Simpson, R. (2012), Kanter Revisited: Gender, Power and (In)Visibility. International Journal of Management Reviews, 14: 141–158., which has been published in final form at http://onlinelibrary.wiley.com/doi/10.1111/j.1468-2370.2011.00327.x/abstract. This paper revisits Kanter's (1977) seminal work Men and Women of the Corporation, rereading her account of numerical advantage and disadvantage through a poststructuralist l...

  13. Kinetics of enzyme-catalyzed cross-linking of feruloylated arabinan from sugar beet

    DEFF Research Database (Denmark)

    Abang Zaidel, Dayang Norulfairuz; Arnous, Anis; Holck, Jesper

    2011-01-01

    the kinetics of HRP catalyzed cross-linking of FA esterified to α-(1,5)-linked arabinans are affected by the length of the arabinan chains carrying the feruloyl substitutions. The kinetics of the HRP-catalyzed cross-linking of four sets of arabinan samples from sugar beet pulp, having different molecular...... weights and hence different degrees of polymerization, were monitored by the disappearance of FA absorbance at 316 nm. MALDI-TOF/TOF-MS analysis confirmed that the sugar beet arabinans were feruloyl-substituted, and HPLC analysis verified that the amounts of diFAs increased when FA levels decreased...

  14. Irreversible processes kinetic theory

    CERN Document Server

    Brush, Stephen G

    2013-01-01

    Kinetic Theory, Volume 2: Irreversible Processes deals with the kinetic theory of gases and the irreversible processes they undergo. It includes the two papers by James Clerk Maxwell and Ludwig Boltzmann in which the basic equations for transport processes in gases are formulated, together with the first derivation of Boltzmann's ""H-theorem"" and a discussion of this theorem, along with the problem of irreversibility.Comprised of 10 chapters, this volume begins with an introduction to the fundamental nature of heat and of gases, along with Boltzmann's work on the kinetic theory of gases and s

  15. Revisit rates and associated costs after an emergency department encounter: a multistate analysis.

    Science.gov (United States)

    Duseja, Reena; Bardach, Naomi S; Lin, Grace A; Yazdany, Jinoos; Dean, Mitzi L; Clay, Theodore H; Boscardin, W John; Dudley, R Adams

    2015-06-02

    Return visits to the emergency department (ED) or hospital after an index ED visit strain the health system, but information about rates and determinants of revisits is limited. To describe revisit rates, variation in revisit rates by diagnosis and state, and associated costs. Observational study using the Healthcare Cost and Utilization Project databases. 6 U.S. states. Adults with ED visits between 2006 and 2010. Revisit rates and costs. Within 3 days of an index ED visit, 8.2% of patients had a revisit; 32% of those revisits occurred at a different institution. Revisit rates varied by diagnosis, with skin infections having the highest rate (23.1% [95% CI, 22.3% to 23.9%]). Revisit rates also varied by state. For skin infections, Florida had higher risk-adjusted revisit rates (24.8% [CI, 23.5% to 26.2%]) than Nebraska (10.6% [CI, 9.2% to 12.1%]). In Florida, the only state with complete cost data, total revisit costs for the 19.8% of patients with a revisit within 30 days were 118% of total index ED visit costs for all patients (including those with and without a revisit). Whether a revisit reflects inadequate access to primary care, a planned revisit, the patient's nonadherence to ED recommendations, or poor-quality care at the initial ED visit remains unknown. Revisits after an index ED encounter are more frequent than previously reported, in part because many occur outside the index institution. Among ED patients in Florida, more resources are spent on revisits than on index ED visits. Agency for Healthcare Research and Quality.

  16. What happened to blood substitutes?

    Science.gov (United States)

    Stowell, C P

    2005-11-01

    Concerns about the safety and adequacy of the blood supply have fostered twenty years of research into the so-called "blood substitutes" among them the oxygen carriers based on modified hemoglobin. Although none of these materials has yet been licensed for use in North America or Europe, the results of research and clinical trials have increased our understanding of oxygen delivery and its regulation. In particular, the examination of the basis for the vasoactivity observed with some of the hemoglobin based oxygen carriers has led to the insight that several colligative properties of hemoglobin solutions, such as their diffusion coefficient for oxygen, viscosity and colloid oncotic pressure, are important determinants of efficacy.

  17. Current status of erythrocyte substitutes.

    Science.gov (United States)

    Biro, G. P.

    1983-01-01

    During the last two decades the search for alternatives to whole blood transfusions has led to promising developments in the field of erythrocyte substitutes. Hemoglobin solutions free of fragments of erythrocyte stroma and fluorocarbon emulsions are not blood-type-specific and appear likely to satisfy some proportion of our blood requirements. Both must be modified before becoming clinically useful. The oxygen affinity of the hemoglobin solution must be reduced and its intravascular persistence improved. Fluorocarbons cannot yet contribute significantly to the oxygen supply unless the patient breathes hyperbaric oxygen. Recent advances are leading to solutions for these problems. PMID:6344974

  18. Biologic and synthetic skin substitutes: An overview

    Directory of Open Access Journals (Sweden)

    Halim Ahmad

    2010-10-01

    Full Text Available The current trend of burn wound care has shifted to more holistic approach of improvement in the long-term form and function of the healed burn wounds and quality of life. This has demanded the emergence of various skin substitutes in the management of acute burn injury as well as post burn reconstructions. Skin substitutes have important roles in the treatment of deep dermal and full thickness wounds of various aetiologies. At present, there is no ideal substitute in the market. Skin substitutes can be divided into two main classes, namely, biological and synthetic substitutes. The biological skin substitutes have a more intact extracellular matrix structure, while the synthetic skin substitutes can be synthesised on demand and can be modulated for specific purposes. Each class has its advantages and disadvantages. The biological skin substitutes may allow the construction of a more natural new dermis and allow excellent re-epithelialisation characteristics due to the presence of a basement membrane. Synthetic skin substitutes demonstrate the advantages of increase control over scaffold composition. The ultimate goal is to achieve an ideal skin substitute that provides an effective and scar-free wound healing.

  19. Chemical Kinetics Database

    Science.gov (United States)

    SRD 17 NIST Chemical Kinetics Database (Web, free access)   The NIST Chemical Kinetics Database includes essentially all reported kinetics results for thermal gas-phase chemical reactions. The database is designed to be searched for kinetics data based on the specific reactants involved, for reactions resulting in specified products, for all the reactions of a particular species, or for various combinations of these. In addition, the bibliography can be searched by author name or combination of names. The database contains in excess of 38,000 separate reaction records for over 11,700 distinct reactant pairs. These data have been abstracted from over 12,000 papers with literature coverage through early 2000.

  20. Thermal kinetic inductance detector

    Science.gov (United States)

    Cecil, Thomas; Gades, Lisa; Miceli, Antonio; Quaranta, Orlando

    2016-12-20

    A microcalorimeter for radiation detection that uses superconducting kinetic inductance resonators as the thermometers. The detector is frequency-multiplexed which enables detector systems with a large number of pixels.

  1. Geometry-controlled kinetics.

    Science.gov (United States)

    Bénichou, O; Chevalier, C; Klafter, J; Meyer, B; Voituriez, R

    2010-06-01

    It has long been appreciated that the transport properties of molecules can control reaction kinetics. This effect can be characterized by the time it takes a diffusing molecule to reach a target-the first-passage time (FPT). Determining the FPT distribution in realistic confined geometries has until now, however, seemed intractable. Here, we calculate this FPT distribution analytically and show that transport processes as varied as regular diffusion, anomalous diffusion, and diffusion in disordered media and fractals, fall into the same universality classes. Beyond the theoretical aspect, this result changes our views on standard reaction kinetics and we introduce the concept of 'geometry-controlled kinetics'. More precisely, we argue that geometry-and in particular the initial distance between reactants in 'compact' systems-can become a key parameter. These findings could help explain the crucial role that the spatial organization of genes has in transcription kinetics, and more generally the impact of geometry on diffusion-limited reactions.

  2. Fundamentals of enzyme kinetics.

    Science.gov (United States)

    Seibert, Eleanore; Tracy, Timothy S

    2014-01-01

    This chapter provides a general introduction to the kinetics of enzyme-catalyzed reactions, with a focus on drug-metabolizing enzymes. A prerequisite to understanding enzyme kinetics is having a clear grasp of the meanings of "enzyme" and "catalysis." Catalysts are reagents that can increase the rate of a chemical reaction without being consumed in the reaction. Enzymes are proteins that form a subset of catalysts. These concepts are further explored below.

  3. Electrochemical kinetics theoretical aspects

    CERN Document Server

    Vetter, Klaus J

    1967-01-01

    Electrochemical Kinetics: Theoretical Aspects focuses on the processes, methodologies, reactions, and transformations in electrochemical kinetics. The book first offers information on electrochemical thermodynamics and the theory of overvoltage. Topics include equilibrium potentials, concepts and definitions, electrical double layer and electrocapillarity, and charge-transfer, diffusion, and reaction overvoltage. Crystallization overvoltage, total overvoltage, and resistance polarization are also discussed. The text then examines the methods of determining electrochemical reaction mechanisms

  4. On the Relativistic Micro-Canonical Ensemble and Relativistic Kinetic Theory for N Relativistic Particles in Inertial and Non-Inertial Rest Frames

    OpenAIRE

    Alba, David; Crater, Horace W.; Lusanna, Luca

    2012-01-01

    A new formulation of relativistic classical mechanics allows a revisiting of old unsolved problems in relativistic kinetic theory and in relativistic statistical mechanics. In particular a definition of the relativistic micro-canonical partition function is given strictly in terms of the Poincar\\'e generators of an interacting N-particle system both in the inertial and non-inertial rest frames. The non-relativistic limit allows a definition of both the inertial and non-inertial micro-canonica...

  5. Comparative Ab-Initio Study of Substituted Norbornadiene-Quadricyclane Compounds for Solar Thermal Storage

    OpenAIRE

    Kuisma, Mikael J.; Lundin, Angelica M.; Moth-Poulsen, Kasper; Hyldgaard, Per; Erhart, Paul

    2016-01-01

    Molecular photoswitches that are capable of storing solar energy, so-called molecular solar thermal storage systems, are interesting candidates for future renewable energy applications. In this context, substituted norbornadiene-quadricyclane systems have received renewed interest due to recent advances in their synthesis. The optical, thermodynamic, and kinetic properties of these systems can vary dramatically depending on the chosen substituents. The molecular design of optimal compounds th...

  6. Palladium-Catalyzed Asymmetric Benzylic Substitution of Secondary Benzyl Carbonates with Nitrogen and Oxygen Nucleophiles.

    Science.gov (United States)

    Najib, Atifah; Hirano, Koji; Miura, Masahiro

    2017-05-05

    A Pd/(R)-BINAP-catalyzed asymmetric benzylic substitution of secondary benzyl carbonates with amides and amines proceeds to form the corresponding optically active benzylamines in good yields with a high enantiomeric ratio. The reaction occurs in a dynamic kinetic asymmetric transformation (DYKAT) manner. Additionally, the asymmetric Pd catalysis can also be applicable to phenol nucleophiles, thus delivering chiral ethers with acceptable yields and enantioselectivity.

  7. Information Technology and Transportation: Substitutes or Complements?

    OpenAIRE

    Oliver, Atara Stephanie

    2013-01-01

    The increased availability and prevalence of Information and Communications Technology (ICT) provides opportunities to use such products as substitutes for transportation. Common examples of this substitution are telecommuting, video conferences, and online classes. However, despite the intuitive appeal of a substitution relationship existing between ICT and transportation, prior research has indicated that the relationship between ICT and transportation is quite complex; at times ICT substit...

  8. cine-Substitution reactions of metallabenzenes: an experimental and computational study.

    Science.gov (United States)

    Wang, Tongdao; Zhang, Hong; Han, Feifei; Long, Lipeng; Lin, Zhenyang; Xia, Haiping

    2013-08-12

    Alkali-resistant osmabenzene [(SCN)2(PPh3)2Os{CHC(PPh3)CHCICH}] (2) can undergo nucleophilic aromatic substitution with MeOH or EtOH to give cine-substitution products [(SCN)2(PPh3)2Os{CHC(PPh3)CHCHCR}] (R=OMe (3), OEt(4)) in the presence of strong alkali. However, the reactions of compound 2 with various amines, such as n-butylamine and aniline, afford five-membered ring species, [(SCN)2(PPh3)2Os{CH=C(PPh3)CH=C(CH=NHR')}] (R'=nBu(8), Ph(9)), in addition to the desired cine-substitution products, [(SCN)2(PPh3)2Os{CHC(PPh3)CHCHC(NHR')}] (R'=nBu(6), Ph(7)), under similar reaction conditions. The mechanisms of these reactions have been investigated in detail with the aid of isotopic labeling experiments and density functional theory (DFT) calculations. The results reveal that the cine-substitution reactions occur through nucleophilic addition, dissociation of the leaving group, protonation, and deprotonation steps, which resemble the classical "addition-of-nucleophile, ring-opening, ring-closure" (ANRORC) mechanism. DFT calculations suggest that, in the reaction with MeOH, the formation of a five-membered metallacycle species is both kinetically and thermodynamically less favorable, which is consistent with the experimental results that only the cine-substitution product is observed. For the analogous reaction with n-butylamine, the pathway for the formation of the cine-substitution product is kinetically less favorable than the pathway for the formation of a five-membered ring species, but is much more thermodynamically favorable, again consistent with the experimental conversion of compound 8 into compound 6, which is observed in an in situ NMR experiment with an isolated pure sample of 8. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Substitutions in Calcium Aluminates and Calcium Aluminoferrites.

    Science.gov (United States)

    ALUMINUM COMPOUNDS, *CEMENTS, * CALCIUM COMPOUNDS, * FERRITES , *SCIENTIFIC RESEARCH, INFRARED SPECTROSCOPY, X RAY DIFFRACTION, CHEMICAL COMPOSITION, SUBSTITUTES, CHEMICAL ANALYSIS, ALKALI METAL COMPOUNDS.

  10. Controversial issues of maternity substitution

    Directory of Open Access Journals (Sweden)

    Andy Pușcă

    2009-06-01

    Full Text Available Substitute maternity consists in a woman carrying a pregnancy (the implant of an embryo, at therequest of a sterile couple, most of the times in exchange of a sum of money, with her commitment tounconditionally give away the newborn after birth to the couple she concluded the agreement with. Manycontroversies emerged in what concerns the contract between the sterile couple and the carrying mother,especially when this contract is by onerous title, which happens in most of the cases. In that a civil contract? Is ita sales contract for the child? Is it a contract to provide services? Is it body marketing? Between total prohibitionand excessive liberalism, the middle way, which is the regulation according to ethical religious, cultural andsocial norms of each community, represents a realistic solution.

  11. Resolution of Reflection Seismic Data Revisited

    DEFF Research Database (Denmark)

    Hansen, Thomas Mejer; Mosegaard, Klaus; Zunino, Andrea

    lower vertical resolution of reflection seismic data. In the following we will revisit think layer model and demonstrate that there is in practice no limit to the vertical resolution using the parameterization of Widess (1973), and that the vertical resolution is limited by the noise in the data...... wavelength of the wavelet within the thin layer. Using a simple thin-layer parameterization Widess (1973) demonstrated that thin layers with thickness less that around λb/8 cannot be resolved from seismic data independent of the noise level. This has results since been widely adopted as a commonly accepted....... In general, we discuss that the resolution of reflection seismic data is controlled by the noise level and the a priori information available...

  12. Revisiting kaon physics in general Z scenario

    Directory of Open Access Journals (Sweden)

    Motoi Endo

    2017-08-01

    Full Text Available New physics contributions to the Z penguin are revisited in the light of the recently-reported discrepancy of the direct CP violation in K→ππ. Interference effects between the standard model and new physics contributions to ΔS=2 observables are taken into account. Although the effects are overlooked in the literature, they make experimental bounds significantly severer. It is shown that the new physics contributions must be tuned to enhance B(KL→π0νν¯, if the discrepancy of the direct CP violation is explained with satisfying the experimental constraints. The branching ratio can be as large as 6×10−10 when the contributions are tuned at the 10% level.

  13. The Faraday effect revisited General theory

    CERN Document Server

    Cornean, H D; Pedersen, T G

    2005-01-01

    This paper is the first in a series revisiting the Faraday effect, or more generally, the theory of electronic quantum transport/optical response in bulk media in the presence of a constant magnetic field. The independent electron approximation is assumed. For free electrons, the transverse conductivity can be explicitly computed and coincides with the classical result. In the general case, using magnetic perturbation theory, the conductivity tensor is expanded in powers of the strength of the magnetic field $B$. Then the linear term in $B$ of this expansion is written down in terms of the zero magnetic field Green function and the zero field current operator. In the periodic case, the linear term in $B$ of the conductivity tensor is expressed in terms of zero magnetic field Bloch functions and energies. No derivatives with respect to the quasimomentum appear and thereby all ambiguities are removed, in contrast to earlier work.

  14. Revisiting monotop production at the LHC

    Energy Technology Data Exchange (ETDEWEB)

    Boucheneb, Idir [Université de Lyon, Université Lyon 1,F-69622 Villeurbanne (France); Cacciapaglia, Giacomo; Deandrea, Aldo [Université de Lyon, Université Lyon 1,F-69622 Villeurbanne (France); Institut de Physique Nucléaire de Lyon, CNRS/IN2P3, UMR5822,F-69622 Villeurbanne Cedex (France); Fuks, Benjamin [CERN, PH-TH,CH-1211 Geneva 23 (Switzerland); Institut Pluridisciplinaire Hubert Curien/Département Recherches Subatomiques,Université de Strasbourg/CNRS-IN2P3, 23 rue du Loess, F-67037 Strasbourg (France)

    2015-01-07

    Scenarios of new physics where a single top quark can be produced in association with large missing energy (monotop) have been recently studied both from the theoretical point of view and by experimental collaborations. We revisit the originally proposed monotop setup by embedding the effective couplings of the top quark in an SU(2){sub L} invariant formalism. We show that minimality selects one model for each of the possible production mechanisms: a scalar field coupling to a right-handed top quark and an invisible fermion when the monotop system is resonantly produced, and a vector field mediating the interactions of a dark sector to right-handed quarks for the non-resonant production mode. We study in detail constraints on the second class of scenarios, originating from contributions to standard single top processes when the mediator is lighter than the top quark and from the dark matter relic abundance when the mediator is heavier than the top quark.

  15. Post-Inflationary Gravitino Production Revisited

    CERN Document Server

    Ellis, John; Nanopoulos, Dimitri V.; Olive, Keith A.; Peloso, Marco

    2016-01-01

    We revisit gravitino production following inflation. As a first step, we review the standard calculation of gravitino production in the thermal plasma formed at the end of post-inflationary reheating when the inflaton has completely decayed. Next we consider gravitino production prior to the completion of reheating, assuming that the inflaton decay products thermalize instantaneously while they are still dilute. We then argue that instantaneous thermalization is in general a good approximation, and also show that the contribution of non-thermal gravitino production via the collisions of inflaton decay products prior to thermalization is relatively small. Our final estimate of the gravitino-to-entropy ratio is approximated well by a standard calculation of gravitino production in the post-inflationary thermal plasma assuming total instantaneous decay and thermalization at a time $t \\simeq 1.2/\\Gamma_\\phi$. Finally, in light of our calculations, we consider potential implications of upper limits on the gravitin...

  16. Damage caps and defensive medicine, revisited.

    Science.gov (United States)

    Paik, Myungho; Black, Bernard; Hyman, David A

    2017-01-01

    Does tort reform reduce defensive medicine and thus healthcare spending? Several (though not all) prior studies, using a difference-in-differences (DiD) approach, find lower Medicare spending for hospital care after states adopt caps on non-economic or total damages ("damage caps"), during the "second" reform wave of the mid-1980s. We re-examine this issue in several ways. We study the nine states that adopted caps during the "third reform wave," from 2002 to 2005. We find that damage caps have no significant impact on Medicare Part A spending, but predict roughly 4% higher Medicare Part B spending. We then revisit the 1980s caps, and find no evidence of a post-adoption drop (or rise) in spending for these caps. Copyright © 2016 Elsevier B.V. All rights reserved.

  17. Mechanism of titanocene-mediated epoxide opening through homolytic substitution

    DEFF Research Database (Denmark)

    Gansäuer, Andreas; Barchuk, Andriy; Keller, Florian

    2007-01-01

    The mechanism of titanocene-mediated epoxide opening was studied by a combination of voltammetric, kinetic, computational, and synthetic methods. With the aid of electrochemical investigations the nature of a number of Ti(III) complexes in solution was established. In particular, the distribution...... of monomeric and dimeric Ti(III) species was found to be strongly affected by the exact steric conditions. The overall rate constants of the reductive epoxide opening were determined for the first time. These data were employed as the basis for computational studies of the structure and energies of the epoxide......−titanocene complexes, the transition states of epoxide opening, and the β-titanoxy radicals formed. The results obtained provide a structural basis for the understanding of the factors determining the regioselectivity of ring opening and match the experimentally determined values. By employing substituted titanocenes...

  18. The size of the sync basin revisited

    Science.gov (United States)

    Delabays, Robin; Tyloo, Melvyn; Jacquod, Philippe

    2017-10-01

    In dynamical systems, the full stability of fixed point solutions is determined by their basins of attraction. Characterizing the structure of these basins is, in general, a complicated task, especially in high dimensionality. Recent works have advocated to quantify the non-linear stability of fixed points of dynamical systems through the relative volumes of the associated basins of attraction [Wiley et al., Chaos 16, 015103 (2006) and Menck et al. Nat. Phys. 9, 89 (2013)]. Here, we revisit this issue and propose an efficient numerical method to estimate these volumes. The algorithm first identifies stable fixed points. Second, a set of initial conditions is considered that are randomly distributed at the surface of hypercubes centered on each fixed point. These initial conditions are dynamically evolved. The linear size of each basin of attraction is finally determined by the proportion of initial conditions which converge back to the fixed point. Armed with this algorithm, we revisit the problem considered by Wiley et al. in a seminal paper [Chaos 16, 015103 (2006)] that inspired the title of the present manuscript and consider the equal-frequency Kuramoto model on a cycle. Fixed points of this model are characterized by an integer winding number q and the number n of oscillators. We find that the basin volumes scale as (1-4 q /n ) n , contrasting with the Gaussian behavior postulated in the study by Wiley et al.. Finally, we show the applicability of our method to complex models of coupled oscillators with different natural frequencies and on meshed networks.

  19. Multiple alternative substrate kinetics.

    Science.gov (United States)

    Anderson, Vernon E

    2015-11-01

    The specificity of enzymes for their respective substrates has been a focal point of enzyme kinetics since the initial characterization of metabolic chemistry. Various processes to quantify an enzyme's specificity using kinetics have been utilized over the decades. Fersht's definition of the ratio kcat/Km for two different substrates as the "specificity constant" (ref [7]), based on the premise that the important specificity existed when the substrates were competing in the same reaction, has become a consensus standard for enzymes obeying Michaelis-Menten kinetics. The expansion of the theory for the determination of the relative specificity constants for a very large number of competing substrates, e.g. those present in a combinatorial library, in a single reaction mixture has been developed in this contribution. The ratio of kcat/Km for isotopologs has also become a standard in mechanistic enzymology where kinetic isotope effects have been measured by the development of internal competition experiments with extreme precision. This contribution extends the theory of kinetic isotope effects to internal competition between three isotopologs present at non-tracer concentrations in the same reaction mix. This article is part of a special issue titled: Enzyme Transition States from Theory and Experiment. Published by Elsevier B.V.

  20. Erbium hydride decomposition kinetics.

    Energy Technology Data Exchange (ETDEWEB)

    Ferrizz, Robert Matthew

    2006-11-01

    Thermal desorption spectroscopy (TDS) is used to study the decomposition kinetics of erbium hydride thin films. The TDS results presented in this report are analyzed quantitatively using Redhead's method to yield kinetic parameters (E{sub A} {approx} 54.2 kcal/mol), which are then utilized to predict hydrogen outgassing in vacuum for a variety of thermal treatments. Interestingly, it was found that the activation energy for desorption can vary by more than 7 kcal/mol (0.30 eV) for seemingly similar samples. In addition, small amounts of less-stable hydrogen were observed for all erbium dihydride films. A detailed explanation of several approaches for analyzing thermal desorption spectra to obtain kinetic information is included as an appendix.

  1. Diffusion Monte Carlo Study of Para-Diiodobenzene Polymorphism Revisited.

    Science.gov (United States)

    Hongo, Kenta; Watson, Mark A; Iitaka, Toshiaki; Aspuru-Guzik, Alán; Maezono, Ryo

    2015-03-10

    We revisit our investigation of the diffusion Monte Carlo (DMC) simulation of para-diiodobenzene (p-DIB) molecular crystal polymorphism. [See J. Phys. Chem. Lett. 2010, 1, 1789-1794.] We perform, for the first time, a rigorous study of finite-size effects and choice of nodal surface on the prediction of polymorph stability in molecular crystals using fixed-node DMC. Our calculations are the largest that are currently feasible using the resources of the K-computer and provide insights into the formidable challenge of predicting such properties from first principles. In particular, we show that finite-size effects can influence the trial nodal surface of a small (1 × 1 × 1) simulation cell considerably. Therefore, we repeated our DMC simulations with a 1 × 3 × 3 simulation cell, which is the largest such calculation to date. We used a density functional theory (DFT) nodal surface generated with the PBE functional, and we accumulated statistical samples with ∼6.4 × 10(5) core hours for each polymorph. Our final results predict a polymorph stability that is consistent with experiment, but they also indicate that the results in our previous paper were somewhat fortuitous. We analyze the finite-size errors using model periodic Coulomb (MPC) interactions and kinetic energy corrections, according to the CCMH scheme of Chiesa, Ceperley, Martin, and Holzmann. We investigate the dependence of the finite-size errors on different aspect ratios of the simulation cell (k-mesh convergence) in order to understand how to choose an appropriate ratio for the DMC calculations. Even in the most expensive simulations currently possible, we show that the finite size errors in the DMC total energies are much larger than the energy difference between the two polymorphs, although error cancellation means that the polymorph prediction is accurate. Finally, we found that the T-move scheme is essential for these massive DMC simulations in order to circumvent population explosions and

  2. Mountain Wave-Induced Turbulence - "Lower Turbulent Zones" Revisited

    Science.gov (United States)

    Strauss, Lukas; Grubišić, Vanda; Serafin, Stefano; Mühlgassner, Rita

    2014-05-01

    In their seminal 1974 paper on "Lower Turbulent Zones Associated with Mountain Lee Waves" P. F. Lester and W. A. Fingerhut attempted to characterize regions of low-level turbulence in the lee of mountain ranges that are commonly associated with large-amplitude mountain waves aloft. For their study, they made extensive use of airborne measurements with small research aircraft that penetrated into the "lower turbulent zone" (LTZ). The Lester and Fingerhut study complemented previous work on wave-induced LTZs by J. P. Kuettner and others in the 1950s who were among the first to employ sailplanes as scientific measurement platforms. Given the limitations of scientific instrumentation on research aircraft in the 1970s (e.g., no GPS) and, in particular, on sailplanes in the 1950s, credit has to be given to these authors for their remarkably detailed account and classification of LTZs. Ever since then, scientists have been trying to refine the conceptual model of the LTZ and shed more light on the origin of turbulence therein. The Terrain-Induced Rotor Experiment (T-REX, Sierra Nevada, California, 2006) is the most recent, major effort organized to investigate the characteristics of LTZs by studying the coupled mountain-wave, rotor, and boundary-layer system. During T-REX, comprehensive ground-based and airborne, in situ and remote sensing measurements were collected during 15 Intensive Observation Periods (IOPs). In this study, we make use of the extensive T-REX datasets to revisit the LTZ concept. During T-REX IOPs, the University of Wyoming King Air (UWKA) research aircraft flew straight-and-level legs aligned with the mean wind direction to document the variation of flow and turbulence over and downwind of the Sierra Nevada. In order to characterize the structure and intensity of turbulence within the LTZ, turbulent kinetic energy (TKE) and eddy-dissipation rate (EDR) were computed from UWKA research flights. In contrast to the rough average values of TKE and EDR

  3. Selective catalytic hydroalkylation and deoxygenation of substituted phenols to bicycloalkanes

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Chen; Camaioni, Donald M.; Lercher, Johannes A.

    2012-04-01

    Phenol and substituted phenols are hydroalkylated and hydrodeoxygenated to bi-cycloalkanes in a tandem reaction over Pd nanoclusters supported on a large-pore molecular sieve HBEA at 473-523 K using water as solvent. The HBEA-supported Pd catalyst (metal-acid ratio: 1:22 mol/mol) optimally balances the competing rates of metal catalyzed hydrogenation as well as of solid acid-catalyzed dehydration and carbon-carbon coupling to combine hydrodeoxygenation and dimerization of phenol derivatives to C{sub 12}-C{sub 18} bicycloalkanes in a single reaction sequence. A detailed kinetic study of the elementary reactions of (substituted) phenol and their potential products (cyclohexanol, cyclohexanone, and cyclohexene) demonstrates that phenol selectively reacts with the in situ generated cyclohexanol or cyclohexene on Broensted acid sites. The acid-catalyzed alkylation of phenol with alcohol intermediates and alcohol dehydration are parallel reactions, which are subtly influenced by the competing hydrogenation reactions as well as by the presence of water as solvent. IR spectroscopy of adsorbed species and preliminary molecular modeling indicate that phenol and cyclohexanol enrichment in the large pores of zeolite HBEA is critical for the high activity and hydroalkylation selectivity.

  4. Tebuconazole photocatalytic degradation kinetics

    OpenAIRE

    Prestes, Thiago de Hermann; Gibbon, Danielle de Oliveira; Lansarin, Marla Azário; Moro, Celso Camilo

    2010-01-01

    The tebuconazole photocatalytic degradation kinetics was studied in a batch reactor using TiO2 (P25-Degussa) as catalyst and a high pressure mercury lamp. The photolysis, adsorption and irradiation effects in the reaction rate were evaluated. Afterward, the suspension catalyst concentration and initial pH to the maximum reaction rate was determined. It was observed that the reaction rate can be approached by a pseudo-first order, with a maximum kinetics constant at 260 mg L-1catalyst concentr...

  5. Type Substitution for Object-Oriented Programming

    DEFF Research Database (Denmark)

    Schwartzbach, Michael Ignatieff; Palsberg, Jens

    1990-01-01

    Genericity allows the substitution of types in a class. This is usually obtained through parameterized classes, although they are inflexible since any class can be inherited but is not in itself parameterized. We suggest a new genericity mechanism, type substitution, which is a subclassing concep...

  6. Educators Take Another Look at Substitutes

    Science.gov (United States)

    Zubrzycki, Jaclyn

    2012-01-01

    The mythology surrounding the substitute teacher is not a pretty one: Paper airplanes, lost learning, bullying. But as schools collect more information about teacher absenteeism and its consequences, districts and schools are exploring ways to professionalize substitute teaching--or experiment with alternative ways of coping with teacher absences.…

  7. 5 CFR 1201.35 - Substituting parties.

    Science.gov (United States)

    2010-01-01

    ... 5 Administrative Personnel 3 2010-01-01 2010-01-01 false Substituting parties. 1201.35 Section... AND PROCEDURES Procedures for Appellate Cases Parties, Representatives, and Witnesses § 1201.35 Substituting parties. (a) If an appellant dies or is otherwise unable to pursue the appeal, the processing of...

  8. 25 CFR 522.9 - Substitute approval.

    Science.gov (United States)

    2010-04-01

    ... 25 Indians 2 2010-04-01 2010-04-01 false Substitute approval. 522.9 Section 522.9 Indians NATIONAL INDIAN GAMING COMMISSION, DEPARTMENT OF THE INTERIOR APPROVAL OF CLASS II AND CLASS III ORDINANCES AND RESOLUTIONS SUBMISSION OF GAMING ORDINANCE OR RESOLUTION § 522.9 Substitute approval. If the Chairman fails to...

  9. Strategic Resource Extraction And Substitute Development

    NARCIS (Netherlands)

    Michielsen, T.O.

    2013-01-01

    Abstract We analyze a dynamic game between a buyer and a seller of an exhaustible resource. The seller chooses resource supply; the buyer can pay a fixed cost to invent a perfect substitute for the resource at any time. In closed-loop equilibrium, the buyer adopts the substitute when the resource is

  10. Substitute Your Way to a Real Job

    Science.gov (United States)

    Stephens, Cathy

    2013-01-01

    For some, substitute teaching is a career choice. However, for the majority of new teachers, it is often a necessary gateway to landing a first job. Either way, it is a great way to sharpen one's skills. This article presents tips from principals, teachers, and human resource directors to make the most of the substitute teaching experience…

  11. Substitute Teachers: Making Lost Days Count

    Science.gov (United States)

    True, Charlene; Butler, Kyle; Sefton, Rachel

    2011-01-01

    As K-12 teachers and administrators grow increasingly concerned with issues of accountability, research-based methods, and intervention strategies, little discussion exists on the impact of substitute teachers in the classroom. In the rush to analyze test scores, are the days covered by substitute teachers even considered? Though districts are…

  12. Multisensory integration, sensory substitution and visual rehabilitation

    DEFF Research Database (Denmark)

    Proulx, Michael J; Ptito, Maurice; Amedi, Amir

    2014-01-01

    Sensory substitution has advanced remarkably over the past 35 years since first introduced to the scientific literature by Paul Bach-y-Rita. In this issue dedicated to his memory, we describe a collection of reviews that assess the current state of neuroscience research on sensory substitution......, visual rehabilitation, and multisensory processes....

  13. Kinetic solvent effects on 1,3-dipolar cycloadditions of benzonitrile oxide

    NARCIS (Netherlands)

    Rispens, T; Engberts, JBFN

    The kinetics of 1,3-dipolar cycloadditions of benzonitrile oxide with a series of N-substituted maleimides and with cyclopentene are reported for water, a wide range of organic solvents and binary solvent mixtures. The results indicate the importance of both solvent polarity and specific

  14. Kinetics of oxygen species in an electrically driven singlet oxygen generator

    Science.gov (United States)

    Azyazov, V. N.; Torbin, A. P.; Pershin, A. A.; Mikheyev, P. A.; Heaven, M. C.

    2015-12-01

    The kinetics of oxygen species in the gaseous medium of a discharge singlet oxygen generator has been revisited. Vibrationally excited ozone O3(υ) formed in O + O2 recombination is thought to be a significant agent in the deactivation of singlet oxygen O2(a1Δ), oxygen atom removal and ozone formation. It is shown that the process O3(υ ⩾ 2) + O2(a1Δ) → 2O2 + O is the main O2(a1Δ) deactivation channel in the post-discharge zone. If no measures are taken to decrease the oxygen atom concentration, the contribution of this process to the overall O2(a1Δ) removal is significant, even in the discharge zone. A simplified model for the kinetics of vibrationally excited ozone is proposed. Calculations based on this model yield results that are in good agreement with the experimental data.

  15. Substitution between cars within the household

    DEFF Research Database (Denmark)

    De Borger, Bruno; Mulalic, Ismir; Rouwendal, Jan

    2016-01-01

    .98 and 1.41 for the primary and secondary cars, respectively. Accounting for substitution effects, these figures reduce to, respectively, 0.32 and 0.45. Consistent with substitution behaviour, we find that the fuel price elasticity of fuel demand exceeds the elasticity of kilometre demands with respect......In this paper we study the demand for car kilometres in two-car households, focusing on the substitution between cars of different fuel efficiency in response to fuel price changes. We use a large sample of detailed Danish data on two-car households to estimate – for each car owned by the household...... – own and cross-price effects of increases in fuel costs per kilometre. The empirical results show that failure to capture substitution between cars within the household can result in substantial misspecification biases. Ignoring substitution, the basic model yielded fuel price elasticities of 0...

  16. Substitution between Cars within the Household

    DEFF Research Database (Denmark)

    de Borger, Bruno; Mulalic, Ismir; Rouwendal, Jan

    In this paper we study the demand for car kilometres in two-car households, focusing on the substitution between cars in response to fuel price changes. We use a large sample of detailed Danish data on two-car households to estimate—for each car owned by the household—own and cross-price effects...... of increases in fuel costs per kilometre. The empirical results show that failure to capture substitution between cars within the household can result in substantial misspecification biases. Ignoring substitution, we estimate fuel price elasticities of –0.81 and -0.65 for the primary and secondary cars......, respectively. When we do take into account the substitution effect, these figures reduce to, respectively, -0.32 and -0.45. We further estimate an alternative version of the model to test the hypothesis that substitution in response to higher fuel prices will be predominantly from the least to the most fuel...

  17. Friction in macroscopic thermodynamics: A kinetic point of view

    Science.gov (United States)

    Bizarro, João P. S.

    2015-12-01

    To provide a solid support to a macroscopic framework developed to explicitly account for friction in thermodynamics, a kinetic description of frictional dissipation is developed. Using either a dissipative Fokker-Planck equation for Brownian motion or a Boltzmann equation with a friction-force term added, it is shown that both approaches lead to the emergence of the macroscopic thermodynamic relations that state the first and second laws with friction. The analysis is directly applied to the problem of determining the minimum amount of heating generated by memory erasure, known in computer science as Landauer's bound, and leads to a better understanding of the energetics behind the latter. A generalisation of Boltzmann's H theorem to include friction explicitly is also recovered, and the thermodynamics of granular rotators acted by a frictional torque and of radio-frequency (RF) current drive of fusion plasmas, in which collisional drag is present, are addressed as well. Various physics results are revisited employing the first and second laws with friction that have been derived from the appropriate dissipative kinetic equations, lower bounds for entropy production rates being derived both for granular rotators and for RF current drive.

  18. Substituted Hydroxyapatites with Antibacterial Properties

    Directory of Open Access Journals (Sweden)

    Joanna Kolmas

    2014-01-01

    Full Text Available Reconstructive surgery is presently struggling with the problem of infections located within implantation biomaterials. Of course, the best antibacterial protection is antibiotic therapy. However, oral antibiotic therapy is sometimes ineffective, while administering an antibiotic at the location of infection is often associated with an unfavourable ratio of dosage efficiency and toxic effect. Thus, the present study aims to find a new factor which may improve antibacterial activity while also presenting low toxicity to the human cells. Such factors are usually implemented along with the implant itself and may be an integral part of it. Many recent studies have focused on inorganic factors, such as metal nanoparticles, salts, and metal oxides. The advantages of inorganic factors include the ease with which they can be combined with ceramic and polymeric biomaterials. The following review focuses on hydroxyapatites substituted with ions with antibacterial properties. It considers materials that have already been applied in regenerative medicine (e.g., hydroxyapatites with silver ions and those that are only at the preliminary stage of research and which could potentially be used in implantology or dentistry. We present methods for the synthesis of modified apatites and the antibacterial mechanisms of various ions as well as their antibacterial efficiency.

  19. Uproar over Milk Substitutes Act.

    Science.gov (United States)

    1993-11-15

    Health policy activists lobbied 7 years for the Infant Milk Substitutes, Feeding Bottles and Infant Food Bill. Proponents of the bill say that it basically curtails unethical marketing practices, not the sales of baby foods, and argue that it was conceived to reduce the trend of mothers over-diluting commercial milk in order to reduce household expenses as well as stem the potential erosion of knowledge on locally available weaning foods. Even though the bill will become an Act only after its rules and regulations have been finalized, the government has already banned baby food advertisements on television and in other electronic media under its control. Women's groups now argue that the bill tends to focus almost exclusively upon the welfare of children and compromises the position of women who can not lactate adequately. Moreover, they hold that the bill may be used to compel wives to stay out of the formal workforce so that they may feed their babies. The intention of the bill may be meaningless without complementary legislation addressing the problems of working mothers. Specifically, amendments to the Maternity Benefits Act of 1961 would extend maternity leave to 4 months after delivery and lengthen the duration of nursing breaks. It is, however, feared that these changes may reduce employment prospects for women.

  20. Kinetic energy budget details

    Indian Academy of Sciences (India)

    Abstract. This paper presents the detailed turbulent kinetic energy budget and higher order statistics of flow behind a surface-mounted rib with and without superimposed acoustic excitation. Pattern recognition technique is used to determine the large-scale structure magnitude. It is observed that most of the turbulence ...

  1. Modeling chemical kinetics graphically

    NARCIS (Netherlands)

    Heck, A.

    2012-01-01

    In literature on chemistry education it has often been suggested that students, at high school level and beyond, can benefit in their studies of chemical kinetics from computer supported activities. Use of system dynamics modeling software is one of the suggested quantitative approaches that could

  2. SHORT COMMUNICATION KINETIC SPECTROPHOTOMETRIC ...

    African Journals Online (AJOL)

    Preferred Customer

    ABSTRACT. ABSTRACT. A novel catalytic kinetic spectrophotometric method for the determination of iron is developed based on the catalytic effect of Fe(III) on the oxidation reaction of p-acetylarsenazo(ASApA) by potassium periodate. Maximum absorbance of the Fe(III)-ASApA-KIO4 system in 8.0 × 10-3 M sulfuric acid ...

  3. CATALYTIC KINETIC SPECTROPHOTOMETRIC DETERMINATION ...

    African Journals Online (AJOL)

    Based on the property that in 0.12 M sulfuric acid medium titanium(IV) catalyzes the discoloring reaction of DBS-arsenazo oxidized by potassium bromate, a new catalytic kinetic spectrophotometric method for the determination of trace titanium (IV) was developed. The linear range of the determination of titanium is

  4. CATALYTIC KINETIC SPECTROPHOTOMETRIC DETERMINATION ...

    African Journals Online (AJOL)

    Preferred Customer

    Research Center for Nanotechnology, Changchun University of Science and Technology,. Changchun 130022 ... Although catalytic kinetic spectrophotometry has been used in the determination of copper, the selectivity ... In this paper CPApA was used as the chromogenic agent, H2O2 as the oxidant, Cu(II) as the catalyst.

  5. Chemical Kinetics, Heat Transfer, and Sensor Dynamics Revisited in a Simple Experiment

    Science.gov (United States)

    Sad, Maria E.; Sad, Mario R.; Castro, Alberto A.; Garetto, Teresita F.

    2008-01-01

    A simple experiment about thermal effects in chemical reactors is described, which can be used to illustrate chemical reactor models, the determination and validation of their parameters, and some simple principles of heat transfer and sensor dynamics. It is based in the exothermic reaction between aqueous solutions of sodium thiosulfate and…

  6. Learning Chemical Kinetics with Spreadsheets.

    Science.gov (United States)

    Blickensderfer, Roger

    1990-01-01

    Presented are several simple kinetic systems together with the spreadsheets used to solve them. A set of exercises in chemical kinetics appropriate for an introductory course in physical chemistry is given. Error propagation calculations with experimental data are illustrated. (CW)

  7. Moessbauer Study of Multiple Substitutions in YBCO

    Energy Technology Data Exchange (ETDEWEB)

    Sarkar, M.; Patel, N. V.; Mehta, P. K.; Somayajulu, D. R. S. [M.S. University, Physics Department (India)

    2001-11-15

    Moessbauer studies of multiple substitutions in YBCO with general formula (Y{sub 1-Z}Ca{sub Z})Ba{sub 2}(Cu{sub 1-X-Y}Fe{sub Y}M{sub X}){sub 3}O{sub 7-{delta}} are reported. XRD has been used to find out the lattice parameters. All the samples show a single tetragonal phase formation. Iodometric titration is done to estimate the oxygen content. The present study discusses the effect of multiple substitutions of 3d-ions like Ni, Zn, Co, Mn, Cr in YBCO and the effect of various substitutions on charge balancing, oxygen content and site occupancy.

  8. Elasticity of Substitution and Antidumping Measures

    DEFF Research Database (Denmark)

    Drud Hansen, Jørgen; Meinen, Philipp; Nielsen, Jørgen Ulff-Møller

    therefore also vary inversely with the elasticity of substitution at least for countries which have a strong focus on prices in the determination of their anti-dumping measures. We test this for ten countries from 1990 to 2009 using data on anti-dumping from Chad Bown (2010) and US-data at 8-digit level......Abstract This paper analyzes the role of the elasticity of substitution for anti-dumping decisions across countries. In monopolistic competition models with cost heterogeneous firms across countries, price differences vary inversely with the elasticity of substitution. Anti-dumping duties should...

  9. Thermochemistry of Hydroxyl and Hydroperoxide Substituted Furan, Methylfuran, and Methoxyfuran.

    Science.gov (United States)

    Hudzik, Jason M; Bozzelli, Joseph W

    2017-06-15

    Reaction pathways are influenced by thermochemical properties, species stability, and chemical kinetics. Understanding these factors allows for an understanding of the reaction paths and formation of intermediate species. Enthalpies of formation (ΔHf,298(°)), entropies (S298(°)), heat capacities (Cp(T)), oxygen-hydrogen (O-H), oxygen-oxygen (O-O), and (R-O) bond dissociation energies (BDEs) are reported for hydroxyl and hydroperoxide substituted furan, methylfuran, and methoxyfuran species. Standard enthalpies of formation for parent and radical species have been determined using density functional theory B3LYP/6-31G(d,p), B3LYP/6-311G(2d,2p), and M06-2X/6-31G(d,p) along with higher-level CBS-QB3 and CBS-APNO composite methods. Isodesmic work reactions were employed to improve accuracy by canceling error and show consistency between the levels of theory. Corresponding O-H and O-O BDEs are determined and compared to other similar structures. The stability of the furan moiety coupled with the double-bond-forming capability of the oxygen moiety results in a number of bond energies significantly lower than one might have expected. Substituted hydroperoxides are calculated to have ROO-H BDEs between 86.9 and 94.2 kcal mol(-1), and their RO-OH BDEs show a large 49 kcal mol(-1) range of -2.3-46.8 kcal mol(-1). Substituted alcohols also show a wide 48 kcal mol(-1) range with RO-H BDEs, ranging from 59.3 to 106.9 kcal mol(-1). Bond lengths of parent and radical species are presented to highlight potential bonds of interest leading to furan ring opening. Group additivity is discussed, and groups for substituted furan, methylfuran, and methoxyfuran species are derived. Structures, moments of inertia, vibrational frequencies, and internal rotor potentials are calculated at the B3LYP/6-31G(d,p) density functional level and are used to determine the S298(°) and Cp(T) values.

  10. Understanding Yield Anomalies in ICF Implosions via Fully Kinetic Simulations

    Science.gov (United States)

    Taitano, William

    2017-10-01

    In the quest towards ICF ignition, plasma kinetic effects are among prime candidates for explaining some significant discrepancies between experimental observations and rad-hydro simulations. To assess their importance, high-fidelity fully kinetic simulations of ICF capsule implosions are needed. Owing to the extremely multi-scale nature of the problem, kinetic codes have to overcome nontrivial numerical and algorithmic challenges, and very few options are currently available. Here, we present resolutions of some long-standing yield discrepancy conundrums using a novel, LANL-developed, 1D-2V Vlasov-Fokker-Planck code iFP. iFP possesses an unprecedented fidelity and features fully implicit time-stepping, exact mass, momentum, and energy conservation, and optimal grid adaptation in phase space, all of which are critically important for ensuring long-time numerical accuracy of the implosion simulations. Specifically, we concentrate on several anomalous yield degradation instances observed in Omega campaigns, with the so-called ``Rygg effect'', or an anomalous yield scaling with the fuel composition, being a prime example. Understanding the physical mechanisms responsible for such degradations in non-ignition-grade Omega experiments is of great interest, as such experiments are often used for platform and diagnostic development, which are then used in ignition-grade experiments on NIF. In the case of Rygg's experiments, effects of a kinetic stratification of fuel ions on the yield have been previously proposed as the anomaly explanation, studied with a kinetic code FPION, and found unimportant. We have revisited this issue with iFP and obtained excellent yield-over-clean agreement with the original Rygg results, and several subsequent experiments. This validates iFP and confirms that the kinetic fuel stratification is indeed at the root of the observed yield degradation. This work was sponsored by the Metropolis Postdoctoral Fellowship, LDRD office, Thermonuclear Burn

  11. Posture Allocation Revisited: Breaking the Sedentary Threshold of Energy Expenditure for Obesity Management

    Directory of Open Access Journals (Sweden)

    Jennifer L. Miles-Chan

    2017-06-01

    Full Text Available There is increasing recognition that low-intensity physical activities of daily life play an important role in achieving energy balance and that their societal erosion through substitution with sedentary (mostly sitting behaviors, whether occupational or for leisure, impact importantly on the obesity epidemic. This has generated considerable interest for better monitoring, characterizing, and promoting countermeasures to sedentariness through a plethora of low-level physical activities (e.g., active workstations, standing desks, sitting breaks, amid the contention that altering posture allocation (lying, sitting, standing can modify energy expenditure to impact upon body weight regulation and health. In addressing this contention, this paper first revisits the past and more recent literature on postural energetics, with particular emphasis on potential determinants of the large inter-individual variability in the energy cost of standing and the impact of posture on fat oxidation. It subsequently analyses the available data pertaining to various strategies by which posture allocations, coupled with light physical activity, may increase energy expenditure beyond the sedentary threshold, and their relevance as potential targets for obesity management.

  12. The Super-GUT CMSSM Revisited

    CERN Document Server

    Ellis, John

    2016-01-01

    We revisit minimal supersymmetric SU(5) grand unification (GUT) models in which the soft supersymmetry-breaking parameters of the minimal supersymmetric Standard Model (MSSM) are universal at some input scale, $M_{in}$, above the supersymmetric gauge coupling unification scale, $M_{GUT}$. As in the constrained MSSM (CMSSM), we assume that the scalar masses and gaugino masses have common values, $m_0$ and $m_{1/2}$ respectively, at $M_{in}$, as do the trilinear soft supersymmetry-breaking parameters $A_0$. Going beyond previous studies of such a super-GUT CMSSM scenario, we explore the constraints imposed by the lower limit on the proton lifetime and the LHC measurement of the Higgs mass, $m_h$. We find regions of $m_0$, $m_{1/2}$, $A_0$ and the parameters of the SU(5) superpotential that are compatible with these and other phenomenological constraints such as the density of cold dark matter, which we assume to be provided by the lightest neutralino. Typically, these allowed regions appear for $m_0$ and $m_{1/...

  13. Searle's"Dualism Revisited"

    Energy Technology Data Exchange (ETDEWEB)

    P., Henry

    2008-11-20

    A recent article in which John Searle claims to refute dualism is examined from a scientific perspective. John Searle begins his recent article 'Dualism Revisited' by stating his belief that the philosophical problem of consciousness has a scientific solution. He then claims to refute dualism. It is therefore appropriate to examine his arguments against dualism from a scientific perspective. Scientific physical theories contain two kinds of descriptions: (1) Descriptions of our empirical findings, expressed in an every-day language that allows us communicate to each other our sensory experiences pertaining to what we have done and what we have learned; and (2) Descriptions of a theoretical model, expressed in a mathematical language that allows us to communicate to each other certain ideas that exist in our mathematical imaginations, and that are believed to represent, within our streams of consciousness, certain aspects of reality that we deem to exist independently of their being perceived by any human observer. These two parts of our scientific description correspond to the two aspects of our general contemporary dualistic understanding of the total reality in which we are imbedded, namely the empirical-mental aspect and the theoretical-physical aspect. The duality question is whether this general dualistic understanding of ourselves should be regarded as false in some important philosophical or scientific sense.

  14. Binocularity and visual search-Revisited.

    Science.gov (United States)

    Zou, Bochao; Utochkin, Igor S; Liu, Yue; Wolfe, Jeremy M

    2017-02-01

    Binocular rivalry is a phenomenon of visual competition in which perception alternates between two monocular images. When two eye's images only differ in luminance, observers may perceive shininess, a form of rivalry called binocular luster. Does dichoptic information guide attention in visual search? Wolfe and Franzel (Perception & Psychophysics, 44(1), 81-93, 1988) reported that rivalry could guide attention only weakly, but that luster (shininess) "popped out," producing very shallow Reaction Time (RT) × Set Size functions. In this study, we have revisited the topic with new and improved stimuli. By using a checkerboard pattern in rivalry experiments, we found that search for rivalry can be more efficient (16 ms/item) than standard, rivalrous grating (30 ms/item). The checkerboard may reduce distracting orientation signals that masked the salience of rivalry between simple orthogonal gratings. Lustrous stimuli did not pop out when potential contrast and luminance artifacts were reduced. However, search efficiency was substantially improved when luster was added to the search target. Both rivalry and luster tasks can produce search asymmetries, as is characteristic of guiding features in search. These results suggest that interocular differences that produce rivalry or luster can guide attention, but these effects are relatively weak and can be hidden by other features like luminance and orientation in visual search tasks.

  15. Pair Production Constraints on Superluminal Neutrinos Revisited

    Energy Technology Data Exchange (ETDEWEB)

    Brodsky, Stanley J.; /SLAC; Gardner, Susan; /Kentucky U.

    2012-02-16

    We revisit the pair creation constraint on superluminal neutrinos considered by Cohen and Glashow in order to clarify which types of superluminal models are constrained. We show that a model in which the superluminal neutrino is effectively light-like can evade the Cohen-Glashow constraint. In summary, any model for which the CG pair production process operates is excluded because such timelike neutrinos would not be detected by OPERA or other experiments. However, a superluminal neutrino which is effectively lightlike with fixed p{sup 2} can evade the Cohen-Glashow constraint because of energy-momentum conservation. The coincidence involved in explaining the SN1987A constraint certainly makes such a picture improbable - but it is still intrinsically possible. The lightlike model is appealing in that it does not violate Lorentz symmetry in particle interactions, although one would expect Hughes-Drever tests to turn up a violation eventually. Other evasions of the CG constraints are also possible; perhaps, e.g., the neutrino takes a 'short cut' through extra dimensions or suffers anomalous acceleration in matter. Irrespective of the OPERA result, Lorentz-violating interactions remain possible, and ongoing experimental investigation of such possibilities should continue.

  16. Revisiting Stephan's Quintet with deep optical images

    Science.gov (United States)

    Duc, Pierre-Alain; Cuillandre, Jean-Charles; Renaud, Florent

    2018-01-01

    Stephan's Quintet, a compact group of galaxies, is often used as a laboratory to study a number of phenomena, including physical processes in the interstellar medium, star formation, galaxy evolution, and the formation of fossil groups. As such, it has been subject to intensive multi-wavelength observation campaigns. Yet, models lack constrains to pin down the role of each galaxy in the assembly of the group. We revisit here this system with multi-band deep optical images obtained with MegaCam on the Canada-France-Hawaii Telescope (CFHT), focusing on the detection of low surface brightness (LSB) structures. They reveal a number of extended LSB features, some new, and some already visible in published images but not discussed before. An extended diffuse, reddish, lopsided, halo is detected towards the early-type galaxy NGC 7317, the role of which had so far been ignored in models. The presence of this halo made of old stars may indicate that the group formed earlier than previously thought. Finally, a number of additional diffuse filaments are visible, some close to the foreground galaxy NGC 7331 located in the same field. Their structure and association with mid-IR emission suggest contamination by emission from Galactic cirrus.

  17. Revisiting the survival mnemonic effect in children.

    Science.gov (United States)

    Pand eirada, Josefa N S; Pires, Luísa; Soares, Sandra C

    2014-04-29

    The survival processing paradigm is designed to explore the adaptive nature of memory functioning. The mnemonic advantage of processing information in fitness-relevant contexts, as has been demonstrated using this paradigm, is now well established, particularly in young adults; this phenomenon is often referred to as the "survival processing effect." In the current experiment, we revisited the investigation of this effect in children and tested it in a new cultural group, using a procedure that differs from the existing studies with children. A group of 40 Portuguese children rated the relevance of unrelated words to a survival and a new moving scenario. This encoding task was followed by a surprise free-recall task. Akin to what is typically found, survival processing produced better memory performance than the control condition (moving). These data put on firmer ground the idea that a mnemonic tuning to fitness-relevant encodings is present early in development. The theoretical importance of this result to the adaptive memory literature is discussed, as well as potential practical implications of this kind of approach to the study of memory in children.

  18. Revisiting the Survival Mnemonic Effect in Children

    Directory of Open Access Journals (Sweden)

    Josefa N. S. Pand Eirada

    2014-04-01

    Full Text Available The survival processing paradigm is designed to explore the adaptive nature of memory functioning. The mnemonic advantage of processing information in fitness-relevant contexts, as has been demonstrated using this paradigm, is now well established, particularly in young adults; this phenomenon is often referred to as the “survival processing effect.” In the current experiment, we revisited the investigation of this effect in children and tested it in a new cultural group, using a procedure that differs from the existing studies with children. A group of 40 Portuguese children rated the relevance of unrelated words to a survival and a new moving scenario. This encoding task was followed by a surprise free-recall task. Akin to what is typically found, survival processing produced better memory performance than the control condition (moving. These data put on firmer ground the idea that a mnemonic tuning to fitness-relevant encodings is present early in development. The theoretical importance of this result to the adaptive memory literature is discussed, as well as potential practical implications of this kind of approach to the study of memory in children.

  19. Revisiting CMB constraints on warm inflation

    Science.gov (United States)

    Arya, Richa; Dasgupta, Arnab; Goswami, Gaurav; Prasad, Jayanti; Rangarajan, Raghavan

    2018-02-01

    We revisit the constraints that Planck 2015 temperature, polarization and lensing data impose on the parameters of warm inflation. To this end, we study warm inflation driven by a single scalar field with a quartic self interaction potential in the weak dissipative regime. We analyse the effect of the parameters of warm inflation, namely, the inflaton self coupling λ and the inflaton dissipation parameter QP on the CMB angular power spectrum. We constrain λ and QP for 50 and 60 number of e-foldings with the full Planck 2015 data (TT, TE, EE + lowP and lensing) by performing a Markov-Chain Monte Carlo analysis using the publicly available code CosmoMC and obtain the joint as well as marginalized distributions of those parameters. We present our results in the form of mean and 68 % confidence limits on the parameters and also highlight the degeneracy between λ and QP in our analysis. From this analysis we show how warm inflation parameters can be well constrained using the Planck 2015 data.

  20. The super-GUT CMSSM revisited

    Energy Technology Data Exchange (ETDEWEB)

    Ellis, John [King' s College London, Theoretical Physics and Cosmology Group, Department of Physics, London (United Kingdom); CERN, Theoretical Physics Department, Geneva (Switzerland); Evans, Jason L. [KIAS, School of Physics, Seoul (Korea, Republic of); Mustafayev, Azar; Nagata, Natsumi; Olive, Keith A. [University of Minnesota, William I. Fine Theoretical Physics Institute, School of Physics and Astronomy, Minneapolis, MN (United States)

    2016-11-15

    We revisit minimal supersymmetric SU(5) grand unification (GUT) models in which the soft supersymmetry-breaking parameters of the minimal supersymmetric Standard Model (MSSM) are universal at some input scale, M{sub in}, above the supersymmetric gauge-coupling unification scale, M{sub GUT}. As in the constrained MSSM (CMSSM), we assume that the scalar masses and gaugino masses have common values, m{sub 0} and m{sub 1/2}, respectively, at M{sub in}, as do the trilinear soft supersymmetry-breaking parameters A{sub 0}. Going beyond previous studies of such a super-GUT CMSSM scenario, we explore the constraints imposed by the lower limit on the proton lifetime and the LHC measurement of the Higgs mass, m{sub h}. We find regions of m{sub 0}, m{sub 1/2}, A{sub 0} and the parameters of the SU(5) superpotential that are compatible with these and other phenomenological constraints such as the density of cold dark matter, which we assume to be provided by the lightest neutralino. Typically, these allowed regions appear for m{sub 0} and m{sub 1/2} in the multi-TeV region, for suitable values of the unknown SU(5) GUT-scale phases and superpotential couplings, and with the ratio of supersymmetric Higgs vacuum expectation values tanβ

  1. Hyperinflation in Brazil, Israel, and Nicaragua revisited

    Science.gov (United States)

    Szybisz, Martín A.; Szybisz, Leszek

    2017-01-01

    The aim of the present work is to address the description of hyperinflation regimens in economy. The spirals of hyperinflation developed in Brazil, Israel, and Nicaragua are revisited. This new analysis of data indicates that the episodes occurred in Brazil and Nicaragua can be understood within the frame of the model available in the literature, which is based on a nonlinear feedback (NLF) characterized by an exponent β > 0. In the NLF model the accumulated consumer price index carries a finite time singularity of the type 1 /(tc - t) (1 - β) / β determining a critical time tc at which the economy would crash. It is shown that in the case of Brazil the entire episode cannot be described with a unique set of parameters because the time series was strongly affected by a change of policy. This fact gives support to the ;so called; Lucas critique, who stated that model's parameters usually change once policy changes. On the other hand, such a model is not able to provide any tc in the case of the weaker hyperinflation occurred in Israel. It is shown that in this case the fit of data yields β → 0. This limit leads to the linear feedback formulation which does not predict any tc. An extension for the NLF model is suggested.

  2. Early-Transition Output Decline Revisited

    Directory of Open Access Journals (Sweden)

    Crt Kostevc

    2016-05-01

    Full Text Available In this paper we revisit the issue of aggregate output decline that took place in the early transition period. We propose an alternative explanation of output decline that is applicable to Central- and Eastern-European countries. In the first part of the paper we develop a simple dynamic general equilibrium model that builds on work by Gomulka and Lane (2001. In particular, we consider price liberalization, interpreted as elimination of distortionary taxation, as a trigger of the output decline. We show that price liberalization in interaction with heterogeneous adjustment costs and non-employment benefits lead to aggregate output decline and surge in wage inequality. While these patterns are consistent with actual dynamics in CEE countries, this model cannot generate output decline in all sectors. Instead sectors that were initially taxed even exhibit output growth. Thus, in the second part we consider an alternative general equilibrium model with only one production sector and two types of labor and distortion in a form of wage compression during the socialist era. The trigger for labor mobility and consequently output decline is wage liberalization. Assuming heterogeneity of workers in terms of adjustment costs and non-employment benefits can explain output decline in all industries.

  3. Meta-analysis in clinical trials revisited.

    Science.gov (United States)

    DerSimonian, Rebecca; Laird, Nan

    2015-11-01

    In this paper, we revisit a 1986 article we published in this Journal, Meta-Analysis in Clinical Trials, where we introduced a random-effects model to summarize the evidence about treatment efficacy from a number of related clinical trials. Because of its simplicity and ease of implementation, our approach has been widely used (with more than 12,000 citations to date) and the "DerSimonian and Laird method" is now often referred to as the 'standard approach' or a 'popular' method for meta-analysis in medical and clinical research. The method is especially useful for providing an overall effect estimate and for characterizing the heterogeneity of effects across a series of studies. Here, we review the background that led to the original 1986 article, briefly describe the random-effects approach for meta-analysis, explore its use in various settings and trends over time and recommend a refinement to the method using a robust variance estimator for testing overall effect. We conclude with a discussion of repurposing the method for Big Data meta-analysis and Genome Wide Association Studies for studying the importance of genetic variants in complex diseases. Published by Elsevier Inc.

  4. Revisiting the argument from fetal potential

    Directory of Open Access Journals (Sweden)

    Manninen Bertha

    2007-05-01

    Full Text Available Abstract One of the most famous, and most derided, arguments against the morality of abortion is the argument from potential, which maintains that the fetus' potential to become a person and enjoy the valuable life common to persons, entails that its destruction is prima facie morally impermissible. In this paper, I will revisit and offer a defense of the argument from potential. First, I will criticize the classical arguments proffered against the importance of fetal potential, specifically the arguments put forth by philosophers Peter Singer and David Boonin, by carefully unpacking the claims made in these arguments and illustrating why they are flawed. Secondly, I will maintain that fetal potential is morally relevant when it comes to the morality of abortion, but that it must be accorded a proper place in the argument. This proper place, however, cannot be found until we first answer a very important and complex question: we must first address the issue of personal identity, and when the fetus becomes the type of being who is relevantly identical to a future person. I will illustrate why the question of fetal potential can only be meaningfully addressed after we have first answered the question of personal identity and how it relates to the human fetus.

  5. Revisiting the relaxation dynamics of isolated pyrrole

    Energy Technology Data Exchange (ETDEWEB)

    Montero, Raúl; Ovejas, Virginia; Fernández-Fernández, Marta; Longarte, Asier, E-mail: asier.longarte@ehu.es [Departamento de Química Física, Universidad del País Vasco (UPV/EHU), Apart. 644, 48080 Bilbao (Spain); Peralta Conde, Álvaro [Centro de Láseres Pulsados (CLPU), Edificio M3, Parque Científico, 37185 Villamayor (Spain)

    2014-07-07

    Herein, the interpretation of the femtosecond-scale temporal evolution of the pyrrole ion signal, after excitation in the 267–217 nm interval, recently published by our group [R. Montero, A. Peralta Conde, V. Ovejas, M. Fernández-Fernández, F. Castaño, J. R. Vázquez de Aldana, and A. Longarte, J. Chem. Phys.137, 064317 (2012)] is re-visited. The observation of a shift in the pyrrole{sup +} transient respect to zero delay reference, initially attributed to ultrafast dynamics on the πσ{sup *} type state (3s a{sub 1} ← π 1a{sub 2}), is demonstrated to be caused by the existence of pump + probe populated states, along the ionization process. The influence of these resonances in pump-prone ionization experiments, when multi-photon probes are used, and the significance of a proper zero-time reference, is discussed. The possibility of preparing the πσ{sup *} state by direct excitation is investigated by collecting 1 + 1 photoelectron spectra, at excitation wavelengths ranging from 255 to 219 nm. No conclusive evidences of ionization through this state are found.

  6. Titmuss and the gift relationship: altruism revisited.

    Science.gov (United States)

    Rapport, F L; Maggs, C J

    2002-12-01

    This paper revisits Richard Titmuss' 1970s blood donation model in the light of its 1997 reprint in order to consider whether we are justified in continuing to accept that the main reason for blood donation (and other donation types) is an altruistic desire to help others. This paper explores how others have examined the notion of altruism, before concentrating on two major elements of Titmuss' work: blood donors' motives to donate and the social implications of gift-giving in relation to the uniqueness of blood donation. Donor motivation is discussed in detail with particular reference to questions 4 and 5 of Titmuss' blood donor survey and through a critical appraisal approach to his work. Methodological inconsistencies are revealed in the design and implementation of the survey, as well as in Titmuss' list of blood donation's unique attributes, bringing into question the rigour of his findings. It may be that blood donors are altruistically motivated, but such conclusions cannot be drawn from this work. It is also unclear if 'altruism' can be shown in the example of blood donation or other donation types. We should reconsider the motivation behind gifting in health care in the light of these findings and ensure that evidence-based practice is consistent with methodological rigour. Nurses and other health professionals need to have a clearer understanding of concepts such as altruism in order to appreciate why people seek to donate.

  7. Revisiting Stephan's Quintet with deep optical images

    Science.gov (United States)

    Duc, Pierre-Alain; Cuillandre, Jean-Charles; Renaud, Florent

    2018-03-01

    Stephan's Quintet, a compact group of galaxies, is often used as a laboratory to study a number of phenomena, including physical processes in the interstellar medium, star formation, galaxy evolution, and the formation of fossil groups. As such, it has been subject to intensive multiwavelength observation campaigns. Yet, models lack constrains to pin down the role of each galaxy in the assembly of the group. We revisit here this system with multiband deep optical images obtained with MegaCam on the Canada-France-Hawaii Telescope (CFHT), focusing on the detection of low surface brightness (LSB) structures. They reveal a number of extended LSB features, some new, and some already visible in published images but not discussed before. An extended diffuse, reddish, lopsided, halo is detected towards the early-type galaxy NGC 7317, the role of which had so far been ignored in models. The presence of this halo made of old stars may indicate that the group formed earlier than previously thought. Finally, a number of additional diffuse filaments are visible, some close to the foreground galaxy NGC 7331 located in the same field. Their structure and association with mid-infrared emission suggest contamination by emission from Galactic cirrus.

  8. Revisiting Twomey's approximation for peak supersaturation

    Directory of Open Access Journals (Sweden)

    B. J. Shipway

    2015-04-01

    Full Text Available Twomey's seminal 1959 paper provided lower and upper bound approximations to the estimation of peak supersaturation within an updraft and thus provides the first closed expression for the number of nucleated cloud droplets. The form of this approximation is simple, but provides a surprisingly good estimate and has subsequently been employed in more sophisticated treatments of nucleation parametrization. In the current paper, we revisit the lower bound approximation of Twomey and make a small adjustment that can be used to obtain a more accurate calculation of peak supersaturation under all potential aerosol loadings and thermodynamic conditions. In order to make full use of this improved approximation, the underlying integro-differential equation for supersaturation evolution and the condition for calculating peak supersaturation are examined. A simple rearrangement of the algebra allows for an expression to be written down that can then be solved with a single lookup table with only one independent variable for an underlying lognormal aerosol population. While multimodal aerosol with N different dispersion characteristics requires 2N+1 inputs to calculate the activation fraction, only N of these one-dimensional lookup tables are needed. No additional information is required in the lookup table to deal with additional chemical, physical or thermodynamic properties. The resulting implementation provides a relatively simple, yet computationally cheap, physically based parametrization of droplet nucleation for use in climate and Numerical Weather Prediction models.

  9. The Einstein-Boltzmann equations revisited

    Science.gov (United States)

    Nadkarni-Ghosh, Sharvari; Refregier, Alexandre

    2017-10-01

    The linear Einstein-Boltzmann (E-B) equations describe the evolution of perturbations in the universe and its numerical solutions play a central role in cosmology. We revisit this system of differential equations and present a detailed investigation of its mathematical properties. For this purpose, we focus on a simplified set of equations aimed at describing the broad features of the matter power spectrum. We first perform an eigenvalue analysis and study the onset of oscillations in the system signalled by the transition from real to complex eigenvalues. We then provide a stability criterion of different numerical schemes for this linear system and estimate the associated step size. We elucidate the stiffness property of the E-B system and show how it can be characterized in terms of the eigenvalues. While the parameters of the system are time dependent making it non-autonomous, we define an adiabatic regime where the parameters vary slowly enough for the system to be quasi-autonomous. We summarize the different regimes of the system for these different criteria as function of wavenumber k and scalefactor a. We also provide a compendium of analytic solutions for all perturbation variables in six limits on the k-a plane and express them explicitly in terms of initial conditions. These results are aimed to help the further development and testing of numerical cosmological Boltzmann solvers.

  10. Photon kinetics in plasmas

    Directory of Open Access Journals (Sweden)

    V.G. Morozov

    2009-01-01

    Full Text Available We present a kinetic theory of radiative processes in many-component plasmas with relativistic electrons and nonrelativistic heavy particles. Using the non-equilibrium Green's function technique in many-particle QED, we show that the transverse field correlation functions can be naturally decomposed into sharply peaked (non-Lorentzian parts that describe resonant (propagating photons and off-shell parts corresponding to virtual photons in the medium. Analogous decompositions are obtained for the longitudinal field correlation functions and the correlation functions of relativistic electrons. We derive a kinetic equation for the resonant photons with a finite spectral width and show that the off-shell parts of the particle and field correlation functions are essential to calculate the local radiating power in plasmas and recover the results of vacuum QED. The plasma effects on radiative processes are discussed.

  11. Kinetics of phase change

    Directory of Open Access Journals (Sweden)

    A.C. Faleiros

    2000-07-01

    Full Text Available The kinetic model for change of phases developed by M. Avrami at the end of the thirties has been used to describe the temporal behavior of phase changes. Until today this model is studied and adapted to include broader hypotheses. However, the mathematical format presented by M. Avrami is difficult to be understood by beginners. The purpose of this work is to clarify the mathematical treatment of Avrami's work, going straightforward to the arguments that led to his main results.

  12. Rapid mixing kinetic techniques.

    Science.gov (United States)

    Martin, Stephen R; Schilstra, Maria J

    2013-01-01

    Almost all of the elementary steps in a biochemical reaction scheme are either unimolecular or bimolecular processes that frequently occur on sub-second, often sub-millisecond, time scales. The traditional approach in kinetic studies is to mix two or more reagents and monitor the changes in concentrations with time. Conventional spectrophotometers cannot generally be used to study reactions that are complete within less than about 20 s, as it takes that amount of time to manually mix the reagents and activate the instrument. Rapid mixing techniques, which generally achieve mixing in less than 2 ms, overcome this limitation. This chapter is concerned with the use of these techniques in the study of reactions which reach equilibrium; the application of these methods to the study of enzyme kinetics is described in several excellent texts (Cornish-Bowden, Fundamentals of enzyme kinetics. Portland Press, 1995; Gutfreund, Kinetics for the life sciences. Receptors, transmitters and catalysis. Cambridge University Press, 1995).There are various ways to monitor changes in concentration of reactants, intermediates and products after mixing, but the most common way is to use changes in optical signals (absorbance or fluorescence) which often accompany reactions. Although absorbance can sometimes be used, fluorescence is often preferred because of its greater sensitivity, particularly in monitoring conformational changes. Such methods are continuous with good time resolution but they seldom permit the direct determination of the concentrations of individual species. Alternatively, samples may be taken from the reaction volume, mixed with a chemical quenching agent to stop the reaction, and their contents assessed by techniques such as HPLC. These methods can directly determine the concentrations of different species, but are discontinuous and have a limited time resolution.

  13. Kinetic transport in crystals

    OpenAIRE

    Marklof, Jens

    2009-01-01

    One of the central challenges in kinetic theory is the derivation of macroscopic evolution equations--describing, for example, the dynamics of an electron gas--from the underlying fundamental microscopic laws of classical or quantum mechanics. An iconic mathematical model in this research area is the Lorentz gas, which describes an ensemble of non-interacting point particles in an infinite array of spherical scatterers. In the case of a disordered scatterer configuration, the classical result...

  14. Transnationalism and integration : complements or Substitutes?

    NARCIS (Netherlands)

    Dekker, B.; Siegel, M.

    2013-01-01

    This paper investigates the relationship between transnational practices and integration by testing whether they are substitutes or complements. For this purpose, we use a multidimensional transnationalism index. The index includes three dimensions of transnational practices, including migrants'

  15. Questioning nuclear waste substitution: a case study.

    Science.gov (United States)

    Marshall, Alan

    2007-03-01

    This article looks at the ethical quandaries, and their social and political context, which emerge as a result of international nuclear waste substitution. In particular it addresses the dilemmas inherent within the proposed return of nuclear waste owned by Japanese nuclear companies and currently stored in the United Kingdom. The UK company responsible for this waste, British Nuclear Fuels Limited (BNFL), wish to substitute this high volume intermediate-level Japanese-owned radioactive waste for a much lower volume of much more highly radioactive waste. Special focus is given to ethical problems that they, and the UK government, have not wished to address as they move forward with waste substitution. The conclusion is that waste substitution can only be considered an ethical practice if a set of moderating conditions are observed by all parties. These conditions are listed and, as of yet, they are not being observed.

  16. DOES CURRENCY SUBSTITUTION AFFECT EXCHANGE RATE VOLATILITY?

    Directory of Open Access Journals (Sweden)

    Hisao Kumamoto

    2014-10-01

    Full Text Available This study investigates the impacts of the degree of currency substitution on nominal exchange rate volatility in seven countries (Indonesia, the Philippines, the Czech Republic, Hungary, Poland, Argentina, and Peru. We use the Threshold ARCH model to consider the ratchet effect of currency substitution and sample periods in the 2000s, during which time the economies of the sample countries stabilized, while the U.S. dollar and euro depreciated against other major currencies following the recent global financial crisis. The presented empirical analyses show that the degree of currency substitution has significant positive effects on the conditional variance of the depreciation rate of the nominal exchange rate in most sample countries. Moreover, a shock to the depreciation rate of the nominal exchange rate has asymmetric effects on the conditional variance, depending on the sign. One possible explanation for these differential effects is the existence of the ratchet effect of currency substitution.

  17. Synthesis of substituted 2-cyanoarylboronic esters

    DEFF Research Database (Denmark)

    Lysén, Morten; Hansen, Henriette M; Begtrup, Mikael

    2006-01-01

    The synthesis of substituted 2-cyanoarylboronic esters is described via lithiation/in situ trapping of the corresponding methoxy-, trifluoromethyl-, fluoro-, chloro-, and bromobenzonitriles. The crude arylboronic esters were obtained in high yields and purities and with good regioselectivities....

  18. Approximate substitutions and the normal ordering problem

    Energy Technology Data Exchange (ETDEWEB)

    Cheballah, H; Duchamp, G H E [Universite Paris 13 Laboratoire d' Informatique Paris Nord, CNRS UMR 7030 99 Av. J-B. Clement, F 93430 Villetaneuse (France); Penson, K A [Laboratoire de Physique Theorique de la Matiere Condensee Universite Pierre et Marie Curie, CNRS UMR 7600 Tour 24 - 2e et., 4 pl. Jussieu, F 75252 Paris Cedex 05 (France)], E-mail: hayat.cheballah@lipn-univ.paris13.fr, E-mail: ghed@lipn-univ.paris13.fr, E-mail: penson@lptl.jussieu.fr

    2008-03-01

    In this paper, we show that the infinite generalised Stirling matrices associated with boson strings with one annihilation operator are projective limits of approximate substitutions, the latter being characterised by a finite set of algebraic equations.

  19. NOVEL PHOSPHAZENE-SUBSTITUTED SILOXANES AND SILANES

    NARCIS (Netherlands)

    VANDEGRAMPEL, JC; JEKEL, AP; PUYENBROEK, R; ARLING, TJ; FRANSEN, W; MEETSMA, A; WUBBELS, JH

    1993-01-01

    Cyclophosphazene-substituted siloxanes and silanes are prepared by the method of hydrosilylation, starting from allyl-derivatized cyclophosphazenes and hydrosiloxanes or hydrosilanes in the presence of a platinum catalyst. Steric and electronic effects govern the course of the reaction.

  20. Substitution within the Danish printing industry

    DEFF Research Database (Denmark)

    Larsen, Henrik Fred; Bøg, Carsten

    2009-01-01

    The implementation of the EU REACH regulation will most probably promote substitution within sectors handling a lot of different chemicals like the printing industry. With the aim of being at the cutting edge of this development the Danish EPA together with the Danish printing industry and IPU...... are running a substitution project. A major part of the work has been mapping the presence of chemicals which are potential candidates for substitution (e.g. PBT, CMR, vPvB, EDS) within the Danish printing industry and this work was recently finished. The mapping comprises a combination of a literature study...... and an investigation of the actual (2007) presence of candidate substances at 15 Danish printing houses including the examination of almost 900 MSDS’s (i.e. products). Furthermore, a focused search in the Danish Product Register has been included. More than 150 of the mapped substances are candidates for substitution...

  1. YL-SUBSTITUTED PHENOLS AND THEIR POTENTIAL ...

    African Journals Online (AJOL)

    nb

    en)yl-substituted phenolic moiety. Alongside this compilation, a diagnostic discussion is presented aiming at pinpointing CNSL phenols as prospective precursors for the semisyntheses of some selected natural products as illustrative examples.

  2. substitution line for resistance to stripe rust

    Indian Academy of Sciences (India)

    2011-08-19

    2D) substitution line for resistance to stripe rust. MENGPING LEI, GUANGRONG LI, SUFEN ZHANG, CHENG LIU and ZUJUN YANG. ∗. School of Life Science and Technology, University of Electronic Science and Technology ...

  3. CHROMIC TRANSITIONS IN PHENYL-SUBSTITUTED ...

    African Journals Online (AJOL)

    a

    substituted polythiophenes were studied. The pristine polymers, upon dissolution in chloroform, exhibited blue-shifted absorption. The solid films of the polymers showed significant blue-shifted as well as red-shifted absorptions when heated.

  4. Kinetic Selectivity of Olefin Metathesis Catalysts Bearing Cyclic (Alkyl)(Amino)Carbenes

    Science.gov (United States)

    Anderson, Donde R.; Ung, Thay; Mkrtumyan, Garik; Bertrand, Guy; Grubbs, Robert H.; Schrodi, Yann

    2008-01-01

    The evaluation of ruthenium olefin metathesis catalysts 4–6 bearing cyclic (alkyl)(amino)carbenes (CAACs) in the cross-metathesis of cis-1,4-diacetoxy-2-butene (7) with allylbenzene (8) and the ethenolysis of methyl oleate (11) is reported. Relative to most NHC-substituted complexes, CAAC-substituted catalysts exhibit lower E/Z ratios (3:1 at 70% conversion) in the cross-metathesis of 7 and 8. Additionally, complexes 4–6 demonstrate good selectivity for the formation of terminal olefins versus internal olefins in the ethenolysis of 11. Indeed, complex 6 achieved 35 000 TONs, the highest recorded to date. CAAC-substituted complexes exhibit markedly different kinetic selectivity than most NHC-substituted complexes. PMID:18584055

  5. Forbidden Synonymous Substitutions in Coding Regions

    OpenAIRE

    Roy J. Britten

    1993-01-01

    In the evolution of highly conserved genes, a few "synonymous" substitutions at third bases that would not alter the protein sequence are forbidden or very rare, presumably as a result of functional requirements of the gene or the messenger RNA. Another 10% or 20% of codons are significantly less variable by synonymous substitution than are the majority of codons. The changes that occur at the majority of third bases are subject to codon usage restrictions. These usage restrictions control se...

  6. Hyperfine magnetic fields in substituted Finemet alloys

    Energy Technology Data Exchange (ETDEWEB)

    Brzózka, K., E-mail: k.brzozka@uthrad.pl [University of Technology and Humanities in Radom, Department of Physics (Poland); Sovák, P. [P.J. Šafárik University, Institute of Physics (Slovakia); Szumiata, T.; Gawroński, M.; Górka, B. [University of Technology and Humanities in Radom, Department of Physics (Poland)

    2016-12-15

    Transmission Mössbauer spectroscopy was used to determine the hyperfine fields of Finemet-type alloys in form of ribbons, substituted alternatively by Mn, Ni, Co, Al, Zn, V or Ge of various concentration. The comparative analysis of magnetic hyperfine fields was carried out which enabled to understand the role of added elements in as-quenched as well as annealed samples. Moreover, the influence of the substitution on the mean direction of the local hyperfine magnetic field was examined.

  7. Enantiospecific Synthesis of β-Substituted Tryptamines.

    Science.gov (United States)

    Rubin, Heather N; Van Hecke, Kinney; Mills, Jonathan J; Cockrell, Jennifer; Morgan, Jeremy B

    2017-09-15

    Functionalized tryptamines are targets of interest for development as small molecule therapeutics. The ring opening of aziridines with indoles is a powerful method for tryptamine synthesis where isomer formation can be controlled. 3,5-Dinitrobenzoyl (DNB)-protected aziridines undergo regioselective, enantiospecific ring opening to produce β-substituted tryptamines for a series of indoles. Attack at the more substituted aziridine carbon occurs in an SN2-like fashion to generate DNB-tryptamine products as synthetic precursors.

  8. Substituting missing data in compositional analysis

    Energy Technology Data Exchange (ETDEWEB)

    Real, Carlos, E-mail: carlos.real@usc.es [Area de Ecologia, Departamento de Biologia Celular y Ecologia, Escuela Politecnica Superior, Universidad de Santiago de Compostela, 27002 Lugo (Spain); Angel Fernandez, J.; Aboal, Jesus R.; Carballeira, Alejo [Area de Ecologia, Departamento de Biologia Celular y Ecologia, Facultad de Biologia, Universidad de Santiago de Compostela, 15782 Santiago de Compostela (Spain)

    2011-10-15

    Multivariate analysis of environmental data sets requires the absence of missing values or their substitution by small values. However, if the data is transformed logarithmically prior to the analysis, this solution cannot be applied because the logarithm of a small value might become an outlier. Several methods for substituting the missing values can be found in the literature although none of them guarantees that no distortion of the structure of the data set is produced. We propose a method for the assessment of these distortions which can be used for deciding whether to retain or not the samples or variables containing missing values and for the investigation of the performance of different substitution techniques. The method analyzes the structure of the distances among samples using Mantel tests. We present an application of the method to PCDD/F data measured in samples of terrestrial moss as part of a biomonitoring study. - Highlights: > Missing values in multivariate data sets must be substituted prior to analysis. > The substituted values can modify the structure of the data set. > We developed a method to estimate the magnitude of the alterations. > The method is simple and based on the Mantel test. > The method allowed the identification of problematic variables in a sample data set. - A method is presented for the assessment of the possible distortions in multivariate analysis caused by the substitution of missing values.

  9. Calcite Dissolution Kinetics

    Science.gov (United States)

    Berelson, W.; Subhas, A.; Dong, S.; Naviaux, J.; Adkins, J. F.

    2016-12-01

    A geological buffer for high atmospheric CO2 concentrations is neutralization via reaction with CaCO3. We have been studying the dissolution kinetics of carbonate minerals using labeled 13C calcite and Picarro-based measurements of 13C enrichments in solution DIC. This methodology has greatly facilitated our investigation of dissolution kinetics as a function of water carbonate chemistry, temperature and pressure. One can adjust the saturation state Omega by changing the ion activity product (e.g. adjusting carbonate ion concentration), or by changing the solubility product (e.g. adjusting temperature or pressure). The canonical formulation of dissolution rate vs. omega has been refined (Subhas et al. 2015) and shows distinct non-linear behavior near equilibrium and rates in sea water of 1-3 e-6 g/cm2day at omega = 0.8. Carbonic anhydrase (CA), an enzyme that catalyzes the hydration of dissolved CO2 to carbonic acid, was shown (in concentrations rate at low degrees of undersaturation by >500x. This result points to the importance of carbonic acid in enhancing dissolution at low degrees of undersaturation. CA activity and abundance in nature must be considered regarding the role it plays in catalyzing dissolution. We also have been investigating the role of temperature on dissolution kinetics. An increase of 16C yields an order of magnitude increase in dissolution rate. Temperature (and P) also change Omega critical, the saturation state where dissolution rates change substantially. Increasing pressure (achieved in a pressure reaction chamber we built) also shifts Omega critical closer to equilibrium and small pressure increases have large impact on dissolution kinetics. Dissolution rates are enhanced by an order of magnitude for a change in pressure of 1500 psi relative to the dissolution rate achieved by water chemistry effects alone for an omega of 0.8. We've shown that the thermodynamic determination of saturation state does not adequately describe the kinetics

  10. Educational Administration and the Management of Knowledge: 1980 Revisited

    Science.gov (United States)

    Bates, Richard

    2013-01-01

    This paper revisits the thesis of a 1980 paper that suggested a new approach to educational administration based upon the New Sociology of Education. In particular it updates answers to the six key questions asked by that paper: what counts as knowledge; how is what counts as knowledge organised; how is what counts as knowledge transmitted; how is…

  11. Revisiting Jack Goody to Rethink Determinisms in Literacy Studies

    Science.gov (United States)

    Collin, Ross

    2013-01-01

    This article revisits Goody's arguments about literacy's influence on social arrangements, culture, cognition, economics, and other domains of existence. Whereas some of his arguments tend toward technological determinism (i.e., literacy causes change in the world), other of his arguments construe literacy as a force that shapes and is shaped by…

  12. Revisiting the Role of Communication in Adolescent Intimate Partner Violence

    Science.gov (United States)

    Messinger, Adam M.; Rickert, Vaughn I.; Fry, Deborah A.; Lessel, Harriet; Davidson, Leslie L.

    2012-01-01

    A growing literature suggests that communication strategies can promote or inhibit intimate partner violence (IPV). Research on communication is still needed on a group ripe for early IPV intervention: high school-aged adolescents. This article revisits our previous analyses of young female reproductive clinic patients (Messinger, Davidson, &…

  13. Revisiting the Gramscian Legacy on Counter-Hegemony, the ...

    African Journals Online (AJOL)

    This article seeks to revisit Gramsci‟s legacy on counter-hegemony, the subaltern and affectivity, by focusing on the implications of his cutting-edge position on the role of subaltern feelings in the formation of an „emotional pedagogy‟ of activism in the context of higher education. Three insights follow from this analysis.

  14. The Legacy of Daantjie Oosthuizen: Revisiting the Liberal Defence ...

    African Journals Online (AJOL)

    canberry

    The Legacy of Daantjie Oosthuizen: Revisiting the Liberal Defence of. Academic Freedom. André du Toit. De part ment of Po lit i cal Studies. Uni ver sity of Cape Town. Cape Town. Intro duction. The classic formu la tions of the liberal notion of academic freedom in the South. African context date from the period of the late ...

  15. A different kind of reformation : Revisiting the Lynn White Thesis

    NARCIS (Netherlands)

    Jedan, Christoph

    2017-01-01

    This commentary revisits Lynn White’s article, ‘The Historical Roots of Our Ecologic Crisis’ (1967), and questions the assumption that there is a unified ‘Lynn White thesis’. Instead, it proposes a complex narrative in which four key elements can be identified: (1) the long history of human impact

  16. Coagulation revisited : Special focus on Prothrombotic states and ...

    African Journals Online (AJOL)

    Adele

    clot . We now have greater insight than ever before on the. Coagulation revisited : Special focus on. Prothrombotic states and anticoagulation. S Mayet degradation of clot and how the different mediators like thrombin , antithrombin and protein C and S act on the cascade. This review aims to provide an overview of the “new”.

  17. Revisiting the teaching of specific language structures in the ...

    African Journals Online (AJOL)

    Revisiting the teaching of specific language structures in the nominal group and the verbal group in English in a second language learning environment. ... nominal group and the verbal group results in the acquisition of knowledge of how ideas can be accessed in the reading of texts, specific reference to academic prose.

  18. Lemba origins revisited: Tracing the ancestry of Y chromosomes in ...

    African Journals Online (AJOL)

    Background. Previous historical, anthropological and genetic data provided overwhelming support for the Semitic origins of the Lemba, a Bantu-speaking people in southern Africa. Objective. To revisit the question concerning genetic affinities between the Lemba and Jews. Methods. Y-chromosome variation was examined ...

  19. Jesus and the law revisited | Loader | HTS Teologiese Studies ...

    African Journals Online (AJOL)

    This article revisited the issue of Jesus' attitude towards the Torah on the basis of a critical discussion of the most recent extensive treatment of the theme by Meier in his A marginal Jew: Rethinking the historical Jesus: Volume four: Law and love (2009). It engaged Meier's contribution in the light of contemporary research, ...

  20. Coccolithophores in Polar Waters: Papposphaera arctica HET and HOL revisited

    DEFF Research Database (Denmark)

    Thomsen, Helge Abildhauge; Heldal, Mikal; Østergaard, Jette B.

    2016-01-01

    It has been generally accepted based on the finding of combination coccospheres in field samples that Turrisphaera arctica and Papposphaera sarion are alternate life-cycle phases of a single species. However, while recently revisiting P. sarion it became evident that the Turrisphaera phase of thi...

  1. "An analysis of the classical Doppler Effect"[1] revisited

    OpenAIRE

    Rothenstein, Bernhard; Nafornita, Corina

    2004-01-01

    After having shown that the formula which describes the Doppler effect in the general case holds only in the case of the "very high" frequency assumption, we derive free of assumptions Doppler formulas for two scenarios presented in the revisited paper.

  2. Thorbecke Revisited : The Role of Doctrinaire Liberalism in Dutch Politics

    NARCIS (Netherlands)

    Drentje, Jan

    2011-01-01

    Thorbecke Revisited: The Role of Doctrinaire Liberalism in Dutch Politics In the political history of the nineteenth century Thorbecke played a crucial role. As the architect of the 1848 liberal constitutional reform he led three cabinets. In many ways he dominated the political discourse during the

  3. Frederick Herzberg\\'s motivation-hygiene theory revisited: The ...

    African Journals Online (AJOL)

    Frederick Herzberg\\'s motivation-hygiene theory revisited: The concept and its applicability to clergy (A study of fulltime stipendiary clergy of the global ... of Wood's (1973) “Faculty Job Satisfaction/Dissatisfaction Scale” was used to measure the satisfaction of clergy relative to Herzberg's satisfier and dissatisfier factors.

  4. Faraday effect revisited: sum rules and convergence issues

    DEFF Research Database (Denmark)

    Cornean, Horia; Nenciu, Gheorghe

    2010-01-01

    This is the third paper of a series revisiting the Faraday effect. The question of the absolute convergence of the sums over the band indices entering the Verdet constant is considered. In general, sum rules and traces per unit volume play an important role in solid-state physics, and they give...

  5. Sleeping sickness in Uganda: revisiting current and historical ...

    African Journals Online (AJOL)

    Sleeping sickness in Uganda: revisiting current and historical distributions. L Berrang-Ford, M Odiit, F Maiso, D Waltner-Toews, J McDermott. Abstract. Background: Sleeping sickness is a parasitic, vector-borne disease, carried by the tsetse fly and prevalent in sub-Saharan Africa. The disease continues to pose a public ...

  6. Living the myth: Revisiting Okigbo's art and commitment

    African Journals Online (AJOL)

    Living the myth: Revisiting Okigbo's art and commitment. This is a study of the nature and sources of the persona's quest in Christopher Okigbo's poetry. The protagonist in Okigbo's writing explores the fluid borders between aesthetic and spiritual states, with language and social action as instruments of the self's aspiration ...

  7. The military glider revisited | Heitman | Scientia Militaria: South ...

    African Journals Online (AJOL)

    Scientia Militaria: South African Journal of Military Studies. Journal Home · ABOUT THIS JOURNAL · Advanced Search · Current Issue · Archives · Journal Home > Vol 12, No 3 (1982) >. Log in or Register to get access to full text downloads. Username, Password, Remember me, or Register. The military glider revisited.

  8. Revisiting Public Health Challenges in the New Millennium | Anish ...

    African Journals Online (AJOL)

    The current article briefly narrates the burden and complexities of challenges faced by the present global health. Revisiting the concept of PHC and reaffirming our solidarity to this philosophy is the need of this hour. Keywords: Asia, Development goals, Millennium, Public health, Public health challenges, Primary healthcare ...

  9. Revisited sunspot numbers and prediction of solar cycle 25

    Science.gov (United States)

    Pishkalo, M.

    2016-06-01

    Parameteres of solar cycles are found usind revisited sunspot numbers in 2015. Correlations between cycle parameters were studied. Solar cycle 25 was predicted using regression equations obtained. I was predicted that minimum and maximum of the cycle (8.3 and 166.7) will occur in May of 2020 and November 2024 to February 2025 respectively.49

  10. Threshold Concepts and Student Engagement: Revisiting Pedagogical Content Knowledge

    Science.gov (United States)

    Zepke, Nick

    2013-01-01

    This article revisits the notion that to facilitate quality learning requires teachers in higher education to have pedagogical content knowledge. It constructs pedagogical content knowledge as a teaching and learning space that brings content and pedagogy together. On the content knowledge side, it suggests that threshold concepts, akin to a…

  11. Revisiting the relevance of economic theory to hotel revenue ...

    African Journals Online (AJOL)

    Revisiting the relevance of economic theory to hotel revenue management education and practice in the era of Big Data. ... Research in Hospitality Management ... This paper explores the role of economics in hospitality education and industry practice, with a particular focus on revenue management, and puts forward an ...

  12. Assesment of mucoadhesion using small deformation rheology revisited

    DEFF Research Database (Denmark)

    Harloff-Helleberg, Stine; Vissing, Karina Juul; Nielsen, Hanne Mørck

    2017-01-01

    This work revisits the commonly used approach to assess mucoadhesion in drug delivery by small deformation rheology. The results show that biosimilar mucus serves as a more predictive mucus model system when compared to mucin suspensions. Data is fitted including error propagation, different from...

  13. Literary Origins of the Term "School Psychologist" Revisited

    Science.gov (United States)

    Fagan, Thomas K.

    2005-01-01

    Previous research on the literary origins of the term "school psychologist" is revisited, and conclusions are revised in light of new evidence. It appears that the origin of the term in the American literature occurred as early as 1898 in an article by Hugo Munsterberg, predating the usage by Wilhelm Stern in 1911. The early references to the…

  14. Revisiting the issue of elite capture in participatory initiatives

    DEFF Research Database (Denmark)

    Lund, Jens Friis; Saito-Jensen, Moeko

    2013-01-01

    Based on case studies of two communities implementing participatory forestry in Tanzania and India, we revisit the issue of elite capture of participatory initiatives. Our cases illustrate how initial elite capture of the participatory initiatives is circumvented over time through various forms...

  15. Revisiting the Continua of Biliteracy: International and Critical Perspectives.

    Science.gov (United States)

    Hornberger, Nancy H.; Skilton-Sylvester, Ellen

    2000-01-01

    The continua model of biliteracy offers a framework to situate research, teaching, and language planning in linguistically diverse settings. The continua model is revisited from the perspective of international cases of educational policy and practice in linguistically diverse settings, and from a critical perspective that seeks to make explicit…

  16. Revisiting deforestation in Africa (1990–2010): One more lost ...

    African Journals Online (AJOL)

    This spotlight revisits the dynamics and prognosis outlined in the late 1980's published in Déforestation en Afrique. This book on deforestation in Africa utilized available statistical data from the 1980's and was a pioneering self - styled attempt to provide a holistic viewpoint of the ongoing trends pertaining to deforestation in ...

  17. Rereading Albert B. Lord's The Singer of Tales . Revisiting the ...

    African Journals Online (AJOL)

    Access to a fresh set of video-recordings of Sesotho praise-poetry made in the year 2000 enabled the author to revisit his adaptation of Albert Lord's definition of the formula as a dynamic compositional device that the oral poet utilizes during delivery. The basic adaptation made in 1983 pertains to heroic praises (dithoko tsa ...

  18. Revisiting the importance of childhood activity | van Rensburg ...

    African Journals Online (AJOL)

    This article revisits the risks of physical inactivity in childhood and provides the latest recommendations for exercise prescription in the paediatric population. Inactive children have a higher risk of developing chronic diseases, such as obesity, type 2 diabetes, high blood cholesterol and hypertension. Other undesirable ...

  19. Stuck Schools Revisited: Beneath the Averages. K-12 Policy

    Science.gov (United States)

    Ushomirsky, Natasha

    2011-01-01

    "Stuck Schools Revisited: Beneath the Averages" shows why a national focus on turning around the lowest performing schools, while needed, is not enough to raise achievement and close gaps. The report analyzes student achievement data from Maryland and Indiana, which reflect the outcomes seen in other states. The results confirm a…

  20. Environmental Education and Politics: Snakes and Ladders Revisited

    Science.gov (United States)

    Chapman, David

    2004-01-01

    This paper revisits the history of environmental education in Australia in the 1970s and 1980s and draws parallels between these and current events in four countries, including Australia. It is argued that little has changed and that few environmental educators confront the inherently political nature of their work. It is concluded that…

  1. Downlink Transmission of Short Packets: Framing and Control Information Revisited

    DEFF Research Database (Denmark)

    Trillingsgaard, Kasper Fløe; Popovski, Petar

    2017-01-01

    Cellular wireless systems rely on frame-based transmissions. The frame design is conventionally based on heuristics, consisting of a frame header and a data part. The frame header contains control information that provides pointers to the messages within the data part. In this paper, we revisit t...

  2. Revisiting Constructivist Teaching Methods in Ontario Colleges Preparing for Accreditation

    Science.gov (United States)

    Schultz, Rachel A.

    2015-01-01

    At the time of writing, the first community colleges in Ontario were preparing for transition to an accreditation model from an audit system. This paper revisits constructivist literature, arguing that a more pragmatic definition of constructivism effectively blends positivist and interactionist philosophies to achieve both student centred…

  3. Bohr’s ‘Light and Life’ revisited

    Science.gov (United States)

    Nussenzveig, H. M.

    2015-11-01

    I revisit Niels Bohr’s famous 1932 ‘Light and Life’ lecture, confronting it with current knowledge. Topics covered include: life origin and evolution, quantum mechanics and life, brain and mind, consciousness and free will, and light as a tool for biology, with special emphasis on optical tweezers and their contributions to biophysics. Specialized knowledge of biology is not assumed.

  4. [Guidelines for substitution treatments in prison populations].

    Science.gov (United States)

    Michel, L; Maguet, O

    2005-01-01

    Care access for the drug addict patients in prison (in particular for the treatments of substitution) in France is very unequal from one establishment to another. This reflects the great variability of the practices of substitution and especially the absence of consensus on the methods of adaptation of these practices to the prison environment. Because of difficulties expressed by prisoners and medical staff on this subject and of stakes (let us recall that approximately 30% of the prisoners are dependent or abusers of one or more psychoactive substances), the formulation of recommendations or of a good practices guide of substitution in prison appeared necessary. Work that we detail here answers a ordering of the Advisory Commission of the Treatments of Substitution (September 2001) whose authors are members. It was presented at the session April 2003. It results from the confrontation of a review of the literature (including legal texts and official reports concerning substitution, the organization of the care in prison environment and the lawful framework), with a vast investigation. The latter was carried out near medical staff (22 prisons), penitentiary staff (3 prisons, 27 people met including directors of these establishments) and prisoners (7 establishments, 28 prisoners met) in the form of individual talks (semi-directing interviews with evaluation of the type of existing device and its knowledge by the penitentiary staff and the prisoners; statement of the suggestions, needs and requests of the medical, penitentiary staffs and of the prisoners). In the whole visited prisons, 7.8% (870) of the prisoners received substitution treatments (6.35% by buprenorphine, 1.44% by methadone), representing a proportion of substituted drug addicts (870 substituted for an evaluation of 3,350 prisoners drug addicts among the 11,168 prisoners of the 22 visited prisons) notably lower than that in free environment (56%, ie 96,000 substituted for an evaluated population of

  5. Kinetic distance and kinetic maps from molecular dynamics simulation

    CERN Document Server

    Noe, Frank

    2015-01-01

    Characterizing macromolecular kinetics from molecular dynamics (MD) simulations requires a distance metric that can distinguish slowly-interconverting states. Here we build upon diffusion map theory and define a kinetic distance for irreducible Markov processes that quantifies how slowly molecular conformations interconvert. The kinetic distance can be computed given a model that approximates the eigenvalues and eigenvectors (reaction coordinates) of the MD Markov operator. Here we employ the time-lagged independent component analysis (TICA). The TICA components can be scaled to provide a kinetic map in which the Euclidean distance corresponds to the kinetic distance. As a result, the question of how many TICA dimensions should be kept in a dimensionality reduction approach becomes obsolete, and one parameter less needs to be specified in the kinetic model construction. We demonstrate the approach using TICA and Markov state model (MSM) analyses for illustrative models, protein conformation dynamics in bovine...

  6. Evolution of large amplitude Alfven waves in solar wind plasmas: Kinetic-fluid models

    Science.gov (United States)

    Nariyuki, Y.

    2014-12-01

    Large amplitude Alfven waves are ubiquitously observed in solar wind plasmas. Mjolhus(JPP, 1976) and Mio et al(JPSJ, 1976) found that nonlinear evolution of the uni-directional, parallel propagating Alfven waves can be described by the derivative nonlinear Schrodinger equation (DNLS). Later, the multi-dimensional extension (Mjolhus and Wyller, JPP, 1988; Passot and Sulem, POP, 1993; Gazol et al, POP, 1999) and ion kinetic modification (Mjolhus and Wyller, JPP, 1988; Spangler, POP, 1989; Medvedev and Diamond, POP, 1996; Nariyuki et al, POP, 2013) of DNLS have been reported. Recently, Nariyuki derived multi-dimensional DNLS from an expanding box model of the Hall-MHD system (Nariyuki, submitted). The set of equations including the nonlinear evolution of compressional wave modes (TDNLS) was derived by Hada(GRL, 1993). DNLS can be derived from TDNLS by rescaling of the variables (Mjolhus, Phys. Scr., 2006). Nariyuki and Hada(JPSJ, 2007) derived a kinetically modified TDNLS by using a simple Landau closure (Hammet and Perkins, PRL, 1990; Medvedev and Diamond, POP, 1996). In the present study, we revisit the ion kinetic modification of multi-dimensional TDNLS through more rigorous derivations, which is consistent with the past kinetic modification of DNLS. Although the original TDNLS was derived in the multi-dimensional form, the evolution of waves with finite propagation angles in TDNLS has not been paid much attention. Applicability of the resultant models to solar wind turbulence is discussed.

  7. Noise processing by microRNA-mediated circuits: The Incoherent Feed-Forward Loop, revisited

    Directory of Open Access Journals (Sweden)

    Silvia Grigolon

    2016-04-01

    Full Text Available The intrinsic stochasticity of gene expression is usually mitigated in higher eukaryotes by post-transcriptional regulation channels that stabilise the output layer, most notably protein levels. The discovery of small non-coding RNAs (miRNAs in specific motifs of the genetic regulatory network has led to identifying noise buffering as the possible key function they exert in regulation. Recent in vitro and in silico studies have corroborated this hypothesis. It is however also known that miRNA-mediated noise reduction is hampered by transcriptional bursting in simple topologies. Here, using stochastic simulations validated by analytical calculations based on van Kampen's expansion, we revisit the noise-buffering capacity of the miRNA-mediated Incoherent Feed Forward Loop (IFFL, a small module that is widespread in the gene regulatory networks of higher eukaryotes, in order to account for the effects of intermittency in the transcriptional activity of the modulator gene. We show that bursting considerably alters the circuit's ability to control static protein noise. By comparing with other regulatory architectures, we find that direct transcriptional regulation significantly outperforms the IFFL in a broad range of kinetic parameters. This suggests that, under pulsatile inputs, static noise reduction may be less important than dynamical aspects of noise and information processing in characterising the performance of regulatory elements.

  8. The time course of photoinactivation of photosystem II in leaves revisited.

    Science.gov (United States)

    Kou, Jiancun; Oguchi, Riichi; Fan, Da-Yong; Chow, Wah Soon

    2012-09-01

    Since photosystem II (PS II) performs the demanding function of water oxidation using light energy, it is susceptible to photoinactivation during photosynthesis. The time course of photoinactivation of PS II yields useful information about the process. Depending on how PS II function is assayed, however, the time course seems to differ. Here, we revisit this problem by using two additional assays: (1) the quantum yield of oxygen evolution in limiting, continuous light and (2) the flash-induced cumulative delivery of PS II electrons to the oxidized primary donor (P700(+)) in PS I measured as a 'P700 kinetics area'. The P700 kinetics area is based on the fact that the two photosystems function in series: when P700 is completely photo-oxidized by a flash added to continuous far-red light, electrons delivered from PS II to PS I by the flash tend to re-reduce P700(+) transiently to an extent depending on the PS II functionality, while the far-red light photo-oxidizes P700 back to the steady-state concentration. The quantum yield of oxygen evolution in limiting, continuous light indeed decreased in a way that deviated from a single-negative exponential. However, measurement of the quantum yield of oxygen in limiting light may be complicated by changes in mitochondrial respiration between darkness and limiting light. Similarly, an assay based on chlorophyll fluorescence may be complicated by the varying depth in leaf tissue from which the signal is detected after progressive photoinactivation of PS II. On the other hand, the P700 kinetics area appears to be a reasonable assay, which is a measure of functional PS II in the whole leaf tissue and independent of changes in mitochondrial respiration. The P700 kinetics area decreased in a single-negative exponential fashion during progressive photoinactivation of PS II in a number of plant species, at least at functional PS II contents ≥6 % of the initial value, in agreement with the conclusion of Sarvikas et al. (Photosynth

  9. 4-Substituted 1-chloo-2-nitrobenzenes: Structure-activity relationships and extension of the subrate model of rat glutathione S-transferase 4-4.

    NARCIS (Netherlands)

    van der Aar, E.M.; de Groot, M.J.; Bouwman, T.; Bijlo, G.J.; Commandeur, J.N.M.; Vermeulen, N.P.E.

    1997-01-01

    In the present study, eleven 4-substituted 1-chloro-2-nitrobenzenes were tested for their GSH conjugation capacity when catalyzed by base or rat glutathione S-transferase (GST) 4-4. Kinetic parameters (k(s) and K(m), k(cat), and k(cat)/K(m)) were determined and subsequently used for the description

  10. NDMA formation by chloramination of ranitidine: Kinetics and mechanism

    KAUST Repository

    Le Roux, Julien

    2012-10-16

    The kinetics of decomposition of the pharmaceutical ranitidine (a major precursor of NDMA) during chloramination was investigated and some decomposition byproducts were identified by using high performance liquid chromatography coupled with mass spectrometry (HPLC-MS). The reaction between monochloramine and ranitidine followed second order kinetics and was acid-catalyzed. Decomposition of ranitidine formed different byproducts depending on the applied monochloramine concentration. Most identified products were chlorinated and hydroxylated analogues of ranitidine. In excess of monochloramine, nucleophilic substitution between ranitidine and monochloramine led to byproducts that are critical intermediates involved in the formation of NDMA, for example, a carbocation formed from the decomposition of the methylfuran moiety of ranitidine. A complete mechanism is proposed to explain the high formation yield of NDMA from chloramination of ranitidine. These results are of great importance to understand the formation of NDMA by chloramination of tertiary amines. © 2012 American Chemical Society.

  11. N = 2 S-duality revisited

    Science.gov (United States)

    Buican, Matthew; Laczko, Zoltan; Nishinaka, Takahiro

    2017-09-01

    Using the chiral algebra bootstrap, we revisit the simplest Argyres-Douglas (AD) generalization of Argyres-Seiberg S-duality. We argue that the exotic AD superconformal field theory (SCFT), T_{3,3/2} , emerging in this duality splits into a free piece and an interacting piece, T_X , even though this factorization seems invisible in the Seiberg-Witten (SW) curve derived from the corresponding M5-brane construction. Without a Lagrangian, an associated topological field theory, a BPS spectrum, or even an SW curve, we nonetheless obtain exact information about T_X by bootstrapping its chiral algebra, {}_X(T_X) , and finding the corresponding vacuum character in terms of Affine Kac-Moody characters. By a standard 4D/2D correspondence, this result gives us the Schur index for T_X and, by studying this quantity in the limit of small S 1, we make contact with a proposed S 1 reduction. Along the way, we discuss various properties of T_X : as an N = 1 theory, it has flavor symmetry SU(3) × SU(2) × U(1), the central charge of {}_X(T_X) matches the central charge of the bc ghosts in bosonic string theory, and its global SU(2) symmetry has a Witten anomaly. This anomaly does not prevent us from building conformal manifolds out of arbitrary numbers of T_X theories (giving us a surprisingly close AD relative of Gaiotto's T N theories), but it does lead to some open questions in the context of the chiral algebra/4D N =2SCFT correspondence.

  12. Solar system anomalies: Revisiting Hubble's law

    Science.gov (United States)

    Plamondon, R.

    2017-12-01

    This paper investigates the impact of a new metric recently published [R. Plamondon and C. Ouellet-Plamondon, in On Recent Developments in Theoretical and Experimental General Relativity, Astrophysics, and Relativistic Field Theories, edited by K. Rosquist, R. T. Jantzen, and R. Ruffini (World Scientific, Singapore, 2015), p. 1301] for studying the space-time geometry of a static symmetric massive object. This metric depends on a complementary error function (erfc) potential that characterizes the emergent gravitation field predicted by the model. This results in two types of deviations as compared to computations made on the basis of a Newtonian potential: a constant and a radial outcome. One key feature of the metric is that it postulates the existence of an intrinsic physical constant σ , the massive object-specific proper length that scales measurements in its surroundings. Although σ must be evaluated experimentally, we use a heuristic to estimate its value and point out some latent relationships between the Hubble constant, the secular increase in the astronomical unit, and the Pioneers delay. Indeed, highlighting the systematic errors that emerge when the effect of σ is neglected, one can link the Hubble constant H 0 to σ Sun and the secular increase V AU to σ Earth . The accuracy of the resulting numerical predictions, H 0 = 74 . 42 ( 0 . 02 ) ( km / s ) / Mpc and V AU ≅ 7.8 cm yr-1 , calls for more investigations of this new metric by specific experts. Moreover, we investigate the expected impacts of the new metric on the flyby anomalies, and we revisit the Pioneers delay. It is shown that both phenomena could be partly taken into account within the context of this unifying paradigm, with quite accurate numerical predictions. A correction for the osculating asymptotic velocity at the perigee of the order of 10 mm/s and an inward radial acceleration of 8 . 34 × 10 - 10 m / s 2 affecting the Pioneer ! space crafts could be explained by this new model.

  13. Kinetics of tetrataenite disordering

    Energy Technology Data Exchange (ETDEWEB)

    Dos Santos, E., E-mail: edisanfi@cbpf.br [Centro Brasileiro de Pesquisas Físicas, Rio de Janeiro (Brazil); Gattacceca, J.; Rochette, P. [Centre Européen de Recherche et d’Enseignement des Géosciences de l’Environnement, UM34, CNRS/Aix-Marseille University, Aix-en-Provence (France); Fillion, G. [Laboratoire National des Champs Magnétiques Intenses (LNCMI), CNRS, UJF, 38042 Grenoble (France); Scorzelli, R.B. [Centro Brasileiro de Pesquisas Físicas, Rio de Janeiro (Brazil)

    2015-02-01

    Tetrataenite is a chemically ordered L1{sub 0}-type Fe{sub 50}Ni{sub 50} alloy detected for the first time in 1977 by {sup 57}Fe Mössbauer spectroscopy studies in iron meteorites. The thermal history of meteorites, in particular short thermal events like those associated to hypervelocity impacts, can be constrained by tracing the presence of tetrataenite or its disordering into taenite. The knowledge of the disordering kinetics of tetrataenite, that is associated with changes in its magnetic properties, is still very fragmentary so that the time–temperature history of these meteorites cannot be constrained in details. Furthermore, knowledge of disordering kinetics is important due to potential technological application of tetrataenite as a rare-earth free strong magnet. Thus, this work provides the first time–temperature data for disordering reaction of tetrataenite. We have shown that disordering is not an instantaneous process but is a kinetic limited reaction. It was shown that disordering may take place at any temperature above the order–disorder transition for L{sub 10} superstructure phase (∼320 °C) when the appropriate time-scale is considered. This result means that the apparent Curie point for tetrataenite is not an absolute property in the sense that any estimate of this parameter should be referred to a given time-scale. - Highlights: • The first time–temperature data for tetrataenite disordering reaction is provided. • Previous works does not give a complete picture of tetrataenite disordering. • Apparent Curie temperature of tetrataenite should be referred to a time-scale. • Tetrataenite can be used as a probe to detect thermal/shock events recorded in meteorites.

  14. Kinetics of stress fibers

    Energy Technology Data Exchange (ETDEWEB)

    Stachowiak, Matthew R; O' Shaughnessy, Ben [Department of Chemical Engineering, Columbia University, New York, NY 10027 (United States)], E-mail: bo8@columbia.edu

    2008-02-15

    Stress fibers are contractile cytoskeletal structures, tensile actomyosin bundles which allow sensing and production of force, provide cells with adjustable rigidity and participate in various processes such as wound healing. The stress fiber is possibly the best characterized and most accessible multiprotein cellular contractile machine. Here we develop a quantitative model of the structure and relaxation kinetics of stress fibers. The principal experimentally known features are incorporated. The fiber has a periodic sarcomeric structure similar to muscle fibers with myosin motor proteins exerting contractile force by pulling on actin filaments. In addition the fiber contains the giant spring-like protein titin. Actin is continuously renewed by exchange with the cytosol leading to a turnover time of several minutes. In order that steady state be possible, turnover must be regulated. Our model invokes simple turnover and regulation mechanisms: actin association and dissociation occur at filament ends, while actin filament overlap above a certain threshold in the myosin-containing regions augments depolymerization rates. We use the model to study stress fiber relaxation kinetics after stimulation, as observed in a recent experimental study where some fiber regions were contractile and others expansive. We find that two distinct episodes ensue after stimulation: the turnover-overlap system relaxes rapidly in seconds, followed by the slow relaxation of sarcomere lengths in minutes. For parameter values as they have been characterized experimentally, we find the long time relaxation of sarcomere length is set by the rate at which actin filaments can grow or shrink in response to the forces exerted by the elastic and contractile elements. Consequently, the stress fiber relaxation time scales inversely with both titin spring constant and the intrinsic actin turnover rate. The model's predicted sarcomere velocities and contraction-expansion kinetics are in good

  15. Chemical kinetics modeling

    Energy Technology Data Exchange (ETDEWEB)

    Westbrook, C.K.; Pitz, W.J. [Lawrence Livermore National Laboratory, CA (United States)

    1993-12-01

    This project emphasizes numerical modeling of chemical kinetics of combustion, including applications in both practical combustion systems and in controlled laboratory experiments. Elementary reaction rate parameters are combined into mechanisms which then describe the overall reaction of the fuels being studied. Detailed sensitivity analyses are used to identify those reaction rates and product species distributions to which the results are most sensitive and therefore warrant the greatest attention from other experimental and theoretical research programs. Experimental data from a variety of environments are combined together to validate the reaction mechanisms, including results from laminar flames, shock tubes, flow systems, detonations, and even internal combustion engines.

  16. A Sequential and Comprehensive Method for Effective Substitute Teaching

    Science.gov (United States)

    Byer, John L.

    2008-01-01

    This article dealt with methods for making substitute teaching more effective. The purpose was to articulate a sequential method for maximizing the effectiveness of substitute teaching while providing substitutes with a comprehensive method for diligently and flexibly earning respect and using reflection to continually improve substitute teaching.…

  17. 12 CFR 229.52 - Substitute check warranties.

    Science.gov (United States)

    2010-01-01

    ... 12 Banks and Banking 3 2010-01-01 2010-01-01 false Substitute check warranties. 229.52 Section 229... SYSTEM AVAILABILITY OF FUNDS AND COLLECTION OF CHECKS (REGULATION CC) Substitute Checks § 229.52 Substitute check warranties. (a) Content and provision of substitute check warranties. A bank that transfers...

  18. 12 CFR 229.51 - General provisions governing substitute checks.

    Science.gov (United States)

    2010-01-01

    ... 12 Banks and Banking 3 2010-01-01 2010-01-01 false General provisions governing substitute checks... FEDERAL RESERVE SYSTEM AVAILABILITY OF FUNDS AND COLLECTION OF CHECKS (REGULATION CC) Substitute Checks § 229.51 General provisions governing substitute checks. (a) Legal equivalence. A substitute check for...

  19. 12 CFR 229.53 - Substitute check indemnity.

    Science.gov (United States)

    2010-01-01

    ... 12 Banks and Banking 3 2010-01-01 2010-01-01 false Substitute check indemnity. 229.53 Section 229... SYSTEM AVAILABILITY OF FUNDS AND COLLECTION OF CHECKS (REGULATION CC) Substitute Checks § 229.53 Substitute check indemnity. (a) Scope of indemnity. A bank that transfers, presents, or returns a substitute...

  20. Acid-base and coordination properties of Meso-substituted porphyrins in nonaqueous solutions

    Science.gov (United States)

    Pukhovskaya, S. G.; Nam, Dao Tkhe; Fien, Chan Ding; Domanina, E. N.; Ivanova, Yu. B.; Semeikin, A. S.

    2017-09-01

    Acid-base and coordination properties of alkyl and aryl meso-substituted porphyrins are studied spectrophotometrically in nonaqueous solutions. It is found that the nature of the substituent greatly affects the basicity of ligands for porphyrins characterized by a flat structure of macrocycle. The electronic effects of substituents have a much weaker influence on the kinetics of complexing. These effects could be due to the opposite orientation of some factors: an increase in the basicity and stability of the N-H bonds of porphyrin reaction centers. Dissociation constants p K b of the cationic forms of meso-substituted derivatives of porphyrin are measured. The values of p K b are in good agreement with classic concepts of the nature of substituents, particularly those indirectly included in the macrocycle through phenyl buffer rings.

  1. 40 CFR 721.1555 - Substituted phenyl azo substituted benzenediazonium salt.

    Science.gov (United States)

    2010-07-01

    ... benzenediazonium salt. 721.1555 Section 721.1555 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... generically as a substituted phenyl azo substituted benzenediazonium salt (PMN P-92-652) is subject to... this part apply to this section except as modified by this paragraph. (1) Recordkeeping. Recordkeeping...

  2. 40 CFR 721.8825 - Substituted methylpyridine and substituted 2-phenoxypyridine.

    Science.gov (United States)

    2010-07-01

    ... respirator fit tests for each person required to wear a respirator. (iii) The names and addresses of persons... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted methylpyridine and substituted 2-phenoxypyridine. 721.8825 Section 721.8825 Protection of Environment ENVIRONMENTAL PROTECTION...

  3. Chemical characterization of some substituted hydroxyapatites

    Directory of Open Access Journals (Sweden)

    Ibrahim Doreya

    2011-11-01

    Full Text Available Abstract Synthetic multi-substituted hydroxyapatite nano powders containing silicon and or carbonate prepared by a wet chemical method. The process parameters are set up to allow the simultaneous substitution of carbonate and silicon ions in the place of phosphorus. The chemical and structural characterizations of the prepared powders are determined with the aid of; XRF, ICP, XRD and FTIR. The results show that, the ion substitution in the crystal lattice of HA caused a change in the unit cell dimensions and affected the degree of crystallization of the produced powders. The apatite formation abilityy of the prepared discs from the synthesized powders is determined by immersing in SBF solution for different periods. The degree of ion release was determined in the obtained solutions. The examined surface of the immersed discs under SEM and analyzed by CDS showed a more dense HA layer than those of un-substituted ones. The HA with the substituted silicon and carbonate ions, showed the highest solubility with greater rate of ion release, compared with carbonate-free powder. All prepared powders took sodium ion from the SBF solution during immersion, which was not recorded before.

  4. Chemical characterization of some substituted hydroxyapatites.

    Science.gov (United States)

    Ibrahim, Doreya Mohamed; Mostafa, Amany A; Korowash, Sara Ibrahim

    2011-11-28

    Synthetic multi-substituted hydroxyapatite nano powders containing silicon and or carbonate prepared by a wet chemical method. The process parameters are set up to allow the simultaneous substitution of carbonate and silicon ions in the place of phosphorus. The chemical and structural characterizations of the prepared powders are determined with the aid of; XRF, ICP, XRD and FTIR. The results show that, the ion substitution in the crystal lattice of HA caused a change in the unit cell dimensions and affected the degree of crystallization of the produced powders. The apatite formation abilityy of the prepared discs from the synthesized powders is determined by immersing in SBF solution for different periods. The degree of ion release was determined in the obtained solutions. The examined surface of the immersed discs under SEM and analyzed by CDS showed a more dense HA layer than those of un-substituted ones. The HA with the substituted silicon and carbonate ions, showed the highest solubility with greater rate of ion release, compared with carbonate-free powder. All prepared powders took sodium ion from the SBF solution during immersion, which was not recorded before.

  5. Kinetics and mechanism of the ligand substitution reaction of di-μ ...

    Indian Academy of Sciences (India)

    effectiveness of the antitumour agent. Diethyldithiocarbamate is an effective chemoprotec- tive agent and is the only chemoprotector effective when administered 1–4h after cisplatin.11,12 More- over the dithiocarbamato derivatives of Pd(II) and. Pt(II) complexes, containing 2,2 -bipyridyl and 1,10- phenanthroline as a ligand ...

  6. Diffusion of substitutional impurities in silicon at short oxidation times: An insight into point defect kinetics

    Science.gov (United States)

    Antoniadis, D. A.; Moskowitz, I.

    1982-10-01

    Oxidation-enhanced diffusion of phosphorus, arsenic, and boron and oxidation-reduced diffusion of antimony in silicon have been studied as a function of oxidation time. Data for the early phase of oxidation in dry oxygen from 5 to 60 min have been obtained. Oxidation-enhanced diffusivities show a steady decrease with decreasing oxidation rate for phosphorus, arsenic, and boron, with enhancements at long oxidation times in agreement with previously reported results. Antimony shows a reduction in diffusivity during oxidation. A model allowing calculation of diffusivity enhancement or reduction for all elements and oxidation times has been developed. The present data support the theory of a dual vacancy-interstitialcy diffusion mechanism for all the elements studied. The fraction of interstitialcy diffusion fI has been calculated, yielding fI=0.38 for phosphorus at 1000 °C, fI=0.30 for boron at 1000 °C, fI=0.35 for arsenic at 1090 °C, and fI=0.015 for antimony at 1100 °C. It has also been shown that the oxidation-induced supersaturation of self-interstitials is accompanied by an undersaturation of vacancies during oxidation. This undersaturation can be explained by a rate-limited bimolecular annihilation mechanism. This theory yields, for the first time, values for the vacancy-interstitial recombination-limited intrinsic vacancy lifetime in silicon under near-equilibrium conditions at high temperature; it also indicates the presence of an energy barrier to this recombination of the order of 1.4 eV.

  7. Kinetic studies on substitution of cis-diaqua-chloro-tris-(dimethyl ...

    Indian Academy of Sciences (India)

    ed.), Inorg. Chem. in. Biol. and Med., (ACS Symp. Ser. 140) Am. Chem. Soc.,. Wasington DC, 157 and references cited therein. 6. Pruchnik P F, Bien M, Lakowicz T and Tadeusz 1996. Met. Based Drugs 4 185. 7. Clarke M J 1980 Met. Ions Biol.

  8. Kinetics of coal pyrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Seery, D.J.; Freihaut, J.D.; Proscia, W.M. (United Technologies Research Center, East Hartford, CT (USA)); Howard, J.B.; Peters, W.; Hsu, J.; Hajaligol, M.; Sarofim, A. (Massachusetts Inst. of Tech., Cambridge, MA (USA)); Jenkins, R.; Mallin, J.; Espindola-Merin, B. (Pennsylvania State Univ., University Park, PA (USA)); Essenhigh, R.; Misra, M.K. (Ohio State Univ., Columbus, OH (USA))

    1989-07-01

    This report contains results of a coordinated, multi-laboratory investigation of coal devolatilization. Data is reported pertaining to the devolatilization for bituminous coals over three orders of magnitude in apparent heating rate (100 to 100,000 + {degree}C/sec), over two orders of magnitude in particle size (20 to 700 microns), final particle temperatures from 400 to 1600{degree}C, heat transfer modes ranging from convection to radiative, ambient pressure ranging from near vacuum to one atmosphere pressure. The heat transfer characteristics of the reactors are reported in detail. It is assumed the experimental results are to form the basis of a devolatilization data base. Empirical rate expressions are developed for each phase of devolatilization which, when coupled to an awareness of the heat transfer rate potential of a particular devolatilization reactor, indicate the kinetics emphasized by a particular system reactor plus coal sample. The analysis indicates the particular phase of devolatilization that will be emphasized by a particular reactor type and, thereby, the kinetic expressions appropriate to that devolatilization system. Engineering rate expressions are developed from the empirical rate expressions in the context of a fundamental understanding of coal devolatilization developed in the course of the investigation. 164 refs., 223 figs., 44 tabs.

  9. Chemical kinetics of gas reactions

    CERN Document Server

    Kondrat'Ev, V N

    2013-01-01

    Chemical Kinetics of Gas Reactions explores the advances in gas kinetics and thermal, photochemical, electrical discharge, and radiation chemical reactions. This book is composed of 10 chapters, and begins with the presentation of general kinetic rules for simple and complex chemical reactions. The next chapters deal with the experimental methods for evaluating chemical reaction mechanisms and some theories of elementary chemical processes. These topics are followed by discussions on certain class of chemical reactions, including unimolecular, bimolecular, and termolecular reactions. The rema

  10. Adsorption analysis equilibria and kinetics

    CERN Document Server

    Do, Duong D

    1998-01-01

    This book covers topics of equilibria and kinetics of adsorption in porous media. Fundamental equilibria and kinetics are dealt with for homogeneous as well as heterogeneous particles. Five chapters of the book deal with equilibria and eight chapters deal with kinetics. Single component as well as multicomponent systems are discussed. In kinetics analysis, we deal with the various mass transport processes and their interactions inside a porous particle. Conventional approaches as well as the new approach using Maxwell-Stefan equations are presented. Various methods to measure diffusivity, such

  11. Revisiting Tversky’s Diagnosticity Principle

    Directory of Open Access Journals (Sweden)

    Ellen R. K. Evers

    2014-08-01

    Full Text Available Similarity is a fundamental concept in cognition. In 1977 Amos Tversky published a highly influential feature-based model of how people judge the similarity between objects. The model highlights the context-dependence of similarity judgments, and challenged geometric models of similarity. One of the context-dependent effects Tversky describes is the diagnosticity principle. The diagnosticity principle determines which features are used to cluster multiple objects into subgroups. Perceived similarity between items within clusters is expected to increase, while similarity between items in different clusters decreases. Here, we present two pre-registered replications of the studies on the diagnosticity effect reported in Tversky, 1977. Additionally, one alternative mechanism that has been proposed to play a role in the original studies, an increase in the choice for distractor items (a substitution effect, see Medin, Goldstone, & Markman, 1995, is examined. Our results replicate those found by Tversky (1977 finding an average diagnosticity-effect of 4.75%. However, when we eliminate the possibility of substitution effects confounding the results, the data provide no indication of any remaining effect of diagnosticity (0.41%, n.s..

  12. Hydra Revisited: Substituting Formal for Self- and Informal In-Home Care among Older Adults with Disabilities

    Science.gov (United States)

    Penning, Margaret J.

    2002-01-01

    Purpose: In response to concerns among policymakers and others that increases in the availability of publicly funded formal services will lead to reductions in self- and informal care, this study examines the relationship between the extent of formal in-home care received and levels of self- and informal care. Design and Methods: Two-stage least…

  13. Vitreous Substitutes: The Present and the Future

    Science.gov (United States)

    Caprani, Simona Maria; Airaghi, Giulia; Bartalena, Luigi; Testa, Francesco; Mariotti, Cesare; Porta, Giovanni; Simonelli, Francesca

    2014-01-01

    Vitreoretinal surgery has advanced in numerous directions during recent years. The removal of the vitreous body is one of the main characteristics of this surgical procedure. Several molecules have been tested in the past to fill the vitreous cavity and to mimic its functions. We here review the currently available vitreous substitutes, focusing on their molecular properties and functions, together with their adverse effects. Afterwards we describe the characteristics of the ideal vitreous substitute. The challenges facing every ophthalmology researcher are to reach a long-term intraocular permanence of vitreous substitute with total inertness of the molecule injected and the control of inflammatory reactions. We report new polymers with gelification characteristics and smart hydrogels representing the future of vitreoretinal surgery. Finally, we describe the current studies on vitreous regeneration and cell cultures to create new intraocular gels with optimal biocompatibility and rheological properties. PMID:24877085

  14. Biomaterials in search of a meniscus substitute.

    Science.gov (United States)

    Rongen, Jan J; van Tienen, Tony G; van Bochove, Bas; Grijpma, Dirk W; Buma, Pieter

    2014-04-01

    The menisci fulfill key biomechanical functions in the tibiofemoral (knee) joint. Unfortunately meniscal injuries are quite common and most often treated by (partial) meniscectomy. However, some patients experience enduring symptoms, and, more importantly, it leads to an increased risk for symptomatic osteoarthritis. Over the past decades, researchers have put effort in developing a meniscal substitute able to prevent osteoarthritis and treat enduring clinical symptoms. Grossly, two categories of substitutes are observed: First, a resorbable scaffold mimicking biomechanical function which slowly degrades while tissue regeneration and organization is promoted. Second, a non resorbable, permanent implant which mimics the biomechanical function of the native meniscus. Numerous biomaterials with different (material) properties have been used in order to provide such a substitute. Nevertheless, a clinically applicable cartilage protecting material is not yet emerged. In the current review we provide an overview, and discuss, these different materials and extract recommendations regarding material properties for future developmental research. Copyright © 2014 Elsevier Ltd. All rights reserved.

  15. New transfusion strategies: red cell substitutes.

    Science.gov (United States)

    Winslow, R M

    1999-01-01

    Red cell substitutes are solutions that can potentially be used in emergencies or during surgery when rapid expansion of the blood volume with an oxygen carrier is needed. The three main types of products in development are based on cell-free hemoglobin, perfluorocarbon emulsions, or liposome-encapsulated hemoglobin. None is currently approved for clinical use, but several are in advanced clinical trials. Outside the red blood cell, hemoglobin is subject to degradation and heme loss. It readily diffuses in the plasma space and effectively scavenges nitric oxide. These properties must be understood and controlled if hemoglobin-based products are to fulfill their promise. The development of red cell substitutes affords us a deeper insight into how oxygen is delivered to tissues in the microcirculation and how blood-flow distribution is regulated within and between organs. As red cell substitutes become available to clinicians and scientists, clinical applications are expected to expand.

  16. A tunable library of substituted thiourea precursors to metal sulfide nanocrystals

    Science.gov (United States)

    Hendricks, Mark P.; Campos, Michael P.; Cleveland, Gregory T.; Jen-La Plante, Ilan; Owen, Jonathan S.

    2015-06-01

    Controlling the size of colloidal nanocrystals is essential to optimizing their performance in optoelectronic devices, catalysis, and imaging applications. Traditional synthetic methods control size by terminating the growth, an approach that limits the reaction yield and causes batch-to-batch variability. Herein we report a library of thioureas whose substitution pattern tunes their conversion reactivity over more than five orders of magnitude and demonstrate that faster thiourea conversion kinetics increases the extent of crystal nucleation. Tunable kinetics thereby allows the nanocrystal concentration to be adjusted and a desired crystal size to be prepared at full conversion. Controlled precursor reactivity and quantitative conversion improve the batch-to-batch consistency of the final nanocrystal size at industrially relevant reaction scales.

  17. A New Substitution Cipher - Random-X

    Directory of Open Access Journals (Sweden)

    Falguni Patel

    2015-08-01

    Full Text Available Ciphers are the encryption methods to prepare the algorithm for encryption and decryption. The currently known ciphers are not strong enough to protect the data. A new substitution cipher Random-X that we introduce in this paper can be used for password encryption and data encryption. Random-X cipher is a unique substitution cipher which replaces the units of plaintext with triplets of letters. The beauty of this cipher is that the encrypted string of the same plain text is not always same. This makes it strong and difficult to crack. This paper covers the principle the implementation ideas and testing of Random-X cipher.

  18. Intramolecular homolytic substitution of sulfinates and sulfinamides.

    Science.gov (United States)

    Coulomb, Julien; Certal, Victor; Larraufie, Marie-Hélène; Ollivier, Cyril; Corbet, Jean-Pierre; Mignani, Gérard; Fensterbank, Louis; Lacôte, Emmanuel; Malacria, Max

    2009-10-05

    A general and efficient method for the synthesis of cyclic sulfinates and sulfinamides based on intramolecular homolytic substitution (S(H)i) at the sulfur atom by aryl or alkyl radicals is described. Both alkyl and benzofused compounds can be accessed directly from easily prepared acyclic precursors. Enantiomerically enriched sulfur-based heterocycles were formed through an S(H)i process with inversion of configuration at the sulfur atom. Cyclization of prochiral radicals proceeded with varying stereochemical outcomes, depending on the size of the incoming radical. 2-Pyridyl and 2-quinolyl radicals led to biaryl compounds, which result from attack onto the ortho position of the arylsulfinate rather than a thiophilic substitution.

  19. A novel kinetic method for the speciation of cadmium in river water by micro solvent extraction with dithizone.

    Science.gov (United States)

    Shimizu, Tokuo; Hiraoka, Yoshinori; Kikuchi, Miyuki; Uehara, Nobuo

    2005-01-01

    Cadmium species in river water were kinetically extracted with dithizone by varying the extraction time. The obtained extraction curve showed a three-stage stepwise profile that reflected the rate of the ligand substitution reaction between the dithizone and cadmium species. Corresponding to each stage, we divided these extracted cadmium species into three groups: "highly labile", "moderately labile" and "slowly labile" species.

  20. Kinetics of Social Contagion

    Science.gov (United States)

    Ruan, Zhongyuan; Iñiguez, Gerardo; Karsai, Márton; Kertész, János

    2015-11-01

    Diffusion of information, behavioral patterns or innovations follows diverse pathways depending on a number of conditions, including the structure of the underlying social network, the sensitivity to peer pressure and the influence of media. Here we study analytically and by simulations a general model that incorporates threshold mechanism capturing sensitivity to peer pressure, the effect of "immune" nodes who never adopt, and a perpetual flow of external information. While any constant, nonzero rate of dynamically introduced spontaneous adopters leads to global spreading, the kinetics by which the asymptotic state is approached shows rich behavior. In particular, we find that, as a function of the immune node density, there is a transition from fast to slow spreading governed by entirely different mechanisms. This transition happens below the percolation threshold of network fragmentation, and has its origin in the competition between cascading behavior induced by adopters and blocking due to immune nodes. This change is accompanied by a percolation transition of the induced clusters.

  1. The temperature hydration kinetics

    Directory of Open Access Journals (Sweden)

    Mircea Oroian

    2017-07-01

    Full Text Available The aim of this study is to evaluate the hydration kinetics of lentil seeds (Lens culinaris in water at different temperatures (25, 32.5, 40, 55, 70 and 80 °C for assessing the adequacy of models for describing the absorption phenomena during soaking. The diffusion coefficient values were calculated using Fick’s model for spherical and hemispherical geometries and the values were in the range of 10−6 m2/s. The experimental data were fitted to Peleg, Sigmoidal, Weibull and Exponential models. The models adequacy was determined using regression coefficients (R2, root mean square error (RMSE and reduced chi-square (χ2. The Peleg model is the suitable one for predicting the experimental data. Temperature had a positive and significant effect on the water absorption capacities and absorption was an endothermic process.

  2. Kinetics of Social Contagion

    CERN Document Server

    Ruan, Zhongyuan; Karsai, Marton; Kertesz, Janos

    2015-01-01

    Diffusion of information, behavioural patterns or innovations follows diverse pathways depending on a number of conditions, including the structure of the underlying social network, the sensitivity to peer pressure and the influence of media. Here we study analytically and by simulations a general model that incorporates threshold mechanism capturing sensitivity to peer pressure, the effect of `immune' nodes who never adopt, and a perpetual flow of external information. While any constant, non-zero rate of dynamically-introduced innovators leads to global spreading, the kinetics by which the asymptotic state is approached show rich behaviour. In particular we find that, as a function of the density of immune nodes, there is a transition from fast to slow spreading governed by entirely different mechanisms. This transition happens below the percolation threshold of fragmentation of the network, and has its origin in the competition between cascading behaviour induced by innovators and blocking of adoption due ...

  3. Photoisomerization kinetics of trifloxystrobin.

    Science.gov (United States)

    Banerjee, Kaushik; Ligon, Axel Patrick; Spiteller, Michael

    2005-08-01

    The photoisomerization kinetics of trifloxystrobin (TFS) in acetone under artificial sunlight is reported. HPLC analysis showed the TFS, a strobilurine fungicide of EE conformation, was converted into an equilibrium mixture of four isomers after illumination for 7 h. The isomers were identified as EZ, EE, ZZ, and ZE and were separated in the crystalline form by preparative HPLC and characterized by use of a variety of spectroscopic techniques. The quantum yield and reaction constants for the isomerization reactions were determined. The detailed spectral features of the individual isomers measured by UV, IR, Raman, NMR and mass spectroscopy are presented and compared. The spectra of the isomers were found to be very characteristic, with good analytical significance.

  4. Substituting freshwater: Can ocean desalination and water recycling capacities substitute for groundwater depletion in California?

    Science.gov (United States)

    Badiuzzaman, Pierre; McLaughlin, Eoin; McCauley, Darren

    2017-12-01

    While the sustainability of resource depletion is a longstanding environmental concern, wider attention has recently been given to growing water scarcity and groundwater depletion. This study seeks to test the substitutability assumption embedded in weak sustainability indicators using a case study of Californian water supply. The volume of groundwater depletion is used as a proxy for unsustainable water consumption, and defined by synthesising existing research estimates into low, medium and high depletion baselines. These are compared against projected water supply increases from ocean desalination and water recycling by 2035, to determine whether new, drought-proof water sources can substitute for currently unsustainable groundwater consumption. Results show that the maximum projected supply of new water, 2.47 million acre-feet per year (MAF/yr), is sufficient to meet low depletion estimates of 2.02 MAF/yr, but fails to come near the high depletion estimate of 3.44 MAF/yr. This does not necessarily indicate physical limitations of substitutability, but more so socio-economic limitations influenced by high comparative costs. By including capacities in demand-substitutability via urban water conservation, maximum predicted capacities reach 5.57 MAF/yr, indicating wide room for substitution. Based on these results, investment in social and institutional capital is an important factor to enhance demand-side substitutability of water and other natural resources, which has been somewhat neglected by the literature on the substitutability of natural resources. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. KINETIC SPECTROPHOTOMETRIC DETERMINATION OF SOME ...

    African Journals Online (AJOL)

    Preferred Customer

    ABSTRACT. A simple and sensitive kinetic spectrophotometric method was developed for the determination of some fluoroquinolonea antibiotics; gemifloxacin mesylate, moxifloxacin hydrochloride and gatifloxacin in bulk and in pharmaceutical preparations. The method is based upon a kinetic investigation of the oxidation ...

  6. Dimensional enhancement of kinetic energies

    DEFF Research Database (Denmark)

    Schleich, W.P.; Dahl, Jens Peder

    2002-01-01

    Simple thermodynamics considers kinetic energy to be an extensive variable which is proportional to the number N of particles. We present a quantum state of N noninteracting particles for which the kinetic energy increases quadratically with N. This enhancement effect is tied to the quantum centr...

  7. The role of brand destination experience in determining revisit intention

    DEFF Research Database (Denmark)

    Mattsson, Jan; Barnes, Stuart; Sørensen, Flemming

    experience, which provides a more holistic and unified view of the brand destination. The research uses a logistic regression model to determine the role of satisfaction and brand experience in determining revisit intentions. The study also examines differences among subgroups and four brand experience sub......-constructs. The findings suggest that brand experience is an important determinant of revisit intentions, but that there is variation among respondent groups. The paper rounds off with conclusions and implications for research and practice.......Destination branding has developed considerably as a topic area in the last decade with numerous conceptualizations focusing on different aspects of the brand. However, a unified view has not yet emerged. This paper examines destination branding via a new conceptualization, brand destination...

  8. The significance test controversy revisited the fiducial Bayesian alternative

    CERN Document Server

    Lecoutre, Bruno

    2014-01-01

    The purpose of this book is not only to revisit the “significance test controversy,”but also to provide a conceptually sounder alternative. As such, it presents a Bayesian framework for a new approach to analyzing and interpreting experimental data. It also prepares students and researchers for reporting on experimental results. Normative aspects: The main views of statistical tests are revisited and the philosophies of Fisher, Neyman-Pearson and Jeffrey are discussed in detail. Descriptive aspects: The misuses of Null Hypothesis Significance Tests are reconsidered in light of Jeffreys’ Bayesian conceptions concerning the role of statistical inference in experimental investigations. Prescriptive aspects: The current effect size and confidence interval reporting practices are presented and seriously questioned. Methodological aspects are carefully discussed and fiducial Bayesian methods are proposed as a more suitable alternative for reporting on experimental results. In closing, basic routine procedures...

  9. L-Lactate-mediated Dynamic Kinetic Resolution of α-Bromo Esters for Asymmetric Syntheses of α-Amino Acid Derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Yelim; Park, Kon Ji; Choi, Yun Soo; Lee, Myungsu; Park, Yong Sun [Konkuk Univ., Seoul (Korea, Republic of)

    2013-08-15

    We conclude that ethyl L-lactate is an effective and convenient chiral auxiliary for dynamic kinetic resolution of α-bromo esters in nucleophilic substitution with various amine nucleophiles. The methodology can provide a general procedure for asymmetric syntheses of dihydroquinoxalinones, dihydrobenzoxazinones and 1,1'-iminodicarboxylic acid derivatives. Simple and easy procedure in obtaining highly enantioenriched α-amino acid derivatives suggests that the dynamic kinetic resolution approach should be further developed. For asymmetric synthesis of α-substituted carboxylic acid derivatives, a variety of chiral auxiliaries have been used for the dynamic resolution of α-halo esters in nucleophilic substitution.1 For example, L-lactamide-mediated dynamic kinetic resolution of α-bromo esters was successfully used for the asymmetric preparation of α-aryloxy carboxylic acids and oxazin-2-ones.

  10. Pornography is No Substitute for Sex.

    Science.gov (United States)

    Parker, Shane

    1998-01-01

    Presents one educator's opinions on the use of computers in foreign-language instruction, as well as in other areas of life in general. He suggests that computers, and particularly CD-ROMs, can be very useful in helping to instruct students, but they are no substitute for one-on-one interactions between students and teachers and should be kept in…

  11. Synthesis of enantiopure 3-substituted morpholines

    DEFF Research Database (Denmark)

    Bornholdt, Jan; Felding, Jakob; Kristensen, Jesper Langgaard

    2010-01-01

    Enantiopure 3-substituted morpholines were assembled through ring-opening of a N-2-benzothiazolesulfonyl (Bts) activated aziridine with organocuprates followed by a ring annulation reaction with a vinylsulfonium salt under microwave conditions. Deprotection of the N-Bts group proceeds under very...

  12. Facile Synthesis of N -Substituted Benzimidazoles

    NARCIS (Netherlands)

    Kurhade, Santosh; Rossetti, Arianna; Dömling, Alexander

    2016-01-01

    A particularly mild and efficient one-pot synthesis of N-substituted benzimidazole derivatives was developed. 2-Fluoro-5-nitrophenylisocyanide reacts with a diverse set of primary amines to afford the respective products in moderate to very good yield (35-95%; 20 examples).

  13. Synthesis and electrochemical studies of phenylazo substituted ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 112; Issue 6. Synthesis and electrochemical studies of phenylazo substituted tetraaza macrocyclic complexes of Ni(II). Randhir Singh Suresh Kumar Amarendra Bhattacharya. Inorganic and Analytical Volume 112 Issue 6 December 2000 pp 601-605 ...

  14. Electromagnetic properties of nanocrystalline Al substituted ...

    Indian Academy of Sciences (India)

    substituted MgCuMn ferrites make them find applications in microwave devices, such as circulators and isolators etc. The applicability of ... sis [3], gas sensors [4], drug delivery [5] and hyperthermia. [6]. The general formula for spinel .... dependence, thus obeying the Vegard's law [15], as given in table 1. The above variation ...

  15. Transparency, Prices and Welfare with Imperfect Substitutes

    NARCIS (Netherlands)

    Boone, J.; Potters, J.J.M.

    2002-01-01

    Markets that are not completely transparent feature complex comparative statics with respect to the effect of number of firms, elasticity of substitution between goods and degree of transparency on equilibrium prices.The main result is that the following 'common wisdom' is incorrect: more

  16. Electrical characterization of zirconium substituted barium titanate ...

    Indian Academy of Sciences (India)

    multilayer capacitors, thermistors and other devices owing to their high dielectric constant. The substitution of ... ionic or mixed electronic–ionic materials and even insula- tors (Macdonald 1987). The resultant ..... Buchanan R C 1991 Principles of electronic ceramics (New York: Marcel Dekker) p. 250. Clarke R and Burfoot ...

  17. Biological activities of substituted trichostatic acid derivatives

    Indian Academy of Sciences (India)

    Administrator

    Abstract. New substituted trichostatic acid derivatives have been synthesized and evaluated for their biological activities towards the H661 non-small lung cancer cell line. These syntheses were achieved by alkylation of propiophenones to introduce the side chain with a terminal precursor of hydroxamic acid.

  18. Biological activities of substituted trichostatic acid derivatives

    Indian Academy of Sciences (India)

    New substituted trichostatic acid derivatives have been synthesized and evaluated for their biological activities towards the H661 non-small lung cancer cell line. These syntheses were achieved by alkylation of propiophenones to introduce the side chain with a terminal precursor of hydroxamic acid and aminobenzamide ...

  19. Preclinical evaluation of injectable bone substitute materials

    NARCIS (Netherlands)

    Bongio, M.; Beucken, J.J.J.P van den; Leeuwenburgh, S.C.G.; Jansen, J.A.

    2015-01-01

    Injectable bone substitutes (IBSs) represent an attractive class of ready-to-use biomaterials, both ceramic- and polymer-based, as they offer the potential benefit of minimally invasive surgery and optimal defect filling. Although in vitro assessments are the first step in the process of

  20. Electrochemical oxidation of substituted benzylamines in aquo ...

    Indian Academy of Sciences (India)

    Electrochemical oxidation of nine para- and meta-substituted benzylamines in varying mole fractions of acetic acid in water has been investigated in the presence of 0.1 M sulphuric acid as supporting electrolyte. The oxidation potentials correlate well with Hammett's substituent constants affording negative reaction ...

  1. Synthesis and biological activities of substituted N ...

    African Journals Online (AJOL)

    use

    2011-12-07

    Dec 7, 2011 ... The present study describes the synthesis, antioxidant and antibacterial activities of substituted N'- benzoylhydrazone ... these derivatives possess promising antioxidant and antibacterial activities, which can be explored for generating new ...... triazole and their divalent nickel complexes. Synth. React. Inorg ...

  2. Photodimerization in pyrimidine-substituted dipeptides

    DEFF Research Database (Denmark)

    Lohse, Brian; Ramanujam, P.S.; Hvilsted, Søren

    2005-01-01

    was compared in aqueous solution: it was dependent on the substitution of the pyrimidine ring. N-alpha,N-alpha'-bis-(uracil-1-ylacetyl)-(N-epsilon-glycylomithineamide) and N-alpha,N-alpha'-bis-(5-bromouracil-1-ylacetyl)-(N-epsilon-glycylomithineamide) were identified as possible candidates for optical data...

  3. Five Strategies to Enhance Your Substitute Teaching

    Science.gov (United States)

    Gresham, Jeanie; Donihoo, John; Cox, Tanisha

    2008-01-01

    Skillful substitute teachers are critical to student achievement, especially in today's high-stakes accountability environment. Because teachers are absent from duty, some for short periods of time and others for lengthy time frames, schools may find it difficult to meet high academic and accountability standards without prepared substitute…

  4. 40 CFR 721.1805 - Substituted bisaniline.

    Science.gov (United States)

    2010-07-01

    ... Section 721.1805 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES... reporting. (1) The chemical substance identified generically as a substituted bisaniline (PMN P-96-1410) is... part apply to this section except as modified by this paragraph. (1) Recordkeeping. Recordkeeping...

  5. 40 CFR 721.1568 - Substituted benzenediazonium.

    Science.gov (United States)

    2010-07-01

    ... Section 721.1568 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES... to reporting. (1) The chemical substance identified generically as a substituted benzenediazonium... subpart A of this part apply to this section except as modified by this paragraph. (1) Recordkeeping...

  6. 40 CFR 721.1900 - Substituted bromothiophene.

    Science.gov (United States)

    2010-07-01

    ... Section 721.1900 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES... reporting. (1) The chemical substance identified generically as substituted bromothiophene (P-83-769) is... this section except as modified by this paragraph. (1) Recordkeeping. The following recordkeeping...

  7. Cadmium substituted high permeability lithium ferrite

    Indian Academy of Sciences (India)

    Unknown

    action becomes weaker than the B–B interaction. This disturbs the parallel arrangement of spin magnetic moments on B-site paving way for canted spins. Zn2+ and Cd2+ substituted ferrites have showed similar type of canting behaviour above a certain limit of their contents. The compositional variation of initial permeability.

  8. Substitution of academically trained by other manpower

    NARCIS (Netherlands)

    J. Tinbergen (Jan)

    1975-01-01

    textabstractSubstitution von Akademikern durch andere ArbeitskrÄfte. — Dieser Aufsatz berichtet über SchÄtzungen von verschiedenen Autoren über die SubstitutionselastizitÄt zwischen hochqualifizierten (meist akademisch ausgebildeten) und anderen ArbeitskrÄften und befaβt sich mit den möglichen

  9. Substitution between cars within the household

    NARCIS (Netherlands)

    de Borger, B.; Mulalic, I.; Rouwendal, J.

    2016-01-01

    In this paper we study the demand for car kilometres in two-car households, focusing on the substitution between cars of different fuel efficiency in response to fuel price changes. We use a large sample of detailed Danish data on two-car households to estimate - for each car owned by the household

  10. Economic implications on management earnings of substituting ...

    African Journals Online (AJOL)

    Economic implications on management earnings of substituting traditional for improved cassava varieties in mix cropping farms in Cross River State. ... A sample of one thousand heads of farms family household across the State were interviewed and their records obtained were analysed following the residual claimant ...

  11. 19 CFR 4.99 - Forms; substitution.

    Science.gov (United States)

    2010-04-01

    ... forms so printed: (1) Conform to the official Customs forms in wording arrangement, style, size of type... 19 Customs Duties 1 2010-04-01 2010-04-01 false Forms; substitution. 4.99 Section 4.99 Customs Duties U.S. CUSTOMS AND BORDER PROTECTION, DEPARTMENT OF HOMELAND SECURITY; DEPARTMENT OF THE TREASURY...

  12. Additive and Substitutive Borrowing against Semantic Broadening ...

    African Journals Online (AJOL)

    The thrust of this paper lies on semantic changes associated with additive and substitutive borrowing in Bantu-speaking communities in Tanzania. Due to contact of languages, semantic differences of the terms related to architectural structures emanate. Apart from data from a few elderly native speakers, research was ...

  13. Scientific Letter: Homemade heroin substitute causing hallucinations ...

    African Journals Online (AJOL)

    Scientific Letter: Homemade heroin substitute causing hallucinations. TI Lemon. Abstract. No Abstracts. African Journal of Psychiatry • November 2013, 16(6). Full Text: EMAIL FREE FULL TEXT EMAIL FREE FULL TEXT · DOWNLOAD FULL TEXT DOWNLOAD FULL TEXT · http://dx.doi.org/10.4314/ajpsy.v16i6.51.

  14. 3-Substituted 2-phenyl-indoles

    DEFF Research Database (Denmark)

    Johansson, Karl Henrik; Jørgensen, T.B.; Gloriam, D.E.

    2013-01-01

    -indoles with a variety of substituents at the indole 3-position. Herein we describe the development of optimised and efficient synthetic routes to a series of new 2-phenyl-indole building blocks 3 to 9 and show that these can be used to generate a broad variety of 3-substituted 2-phenyl-indoles of interest to medicinal...

  15. Towards hemerythrin-based blood substitutes: Comparative ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Biosciences; Volume 36; Issue 2. Towards hemerythrin-based blood substitutes: Comparative performance to hemoglobin on human leukocytes and umbilical vein endothelial cells. Eva Fischer-Fodor Augustin Mot Florina Deac Mariann Arkosi Radu Silaghi-Dumitrescu. Brief communication ...

  16. Gd-substituted Bi-2223 superconductor

    Indian Academy of Sciences (India)

    Various researchers, who have studied the effect of doping in Bi-based high-Tc superconductors, seem to ... mum temperature for the sintering of the complete series of gadolinium-substituted. (BiPb)-2223 specimens. ..... support (senior research fellowship) and facilities for the work to be carried out. References. [1] V P S ...

  17. Fossil Fuels, Backstop Technologies, and Imperfect Substitution

    NARCIS (Netherlands)

    van der Meijden, G.C.; Pittel, Karen; van der Ploeg, Frederick; Withagen, Cees

    2014-01-01

    This chapter studies the transition from fossil fuels to backstop technologies in a general equilibrium model in which growth is driven by research and development. The analysis generalizes the existing literature by allowing for imperfect substitution between fossil fuels and the new energy

  18. Substitute fluid examinations for liquid manure

    Science.gov (United States)

    Schrader, Kevin; Riedel, Marco; Eichert, Helmut

    For the farming industry it is essential to use liquid manure as natural fertilizer. Through new agricultural regulation 2015 in Germany the industry must develop new liquid manure spreader systems because the ammonia and methane emission are limited. In a research project the University of Applied Sciences Zwickau and some other industry partners will develop such a new innovative liquid manure spreader. The new liquid manure spreader should use pulsating air to distribute the liquid manure exactly. The pulsating air, which flows through the pipelines, should be analysed at a test station. For examinations at this test station it is important to find another substitute fluid because liquid manure smells strong, is not transparent and is also not homogeneous enough for scientific investigations. Furthermore it is important to ensure that the substitute fluid is, like liquid manure, a non-Newtonian fluid. The substitute fluid must be a shear-thinning substance - this means the viscosity decrease at higher shear rate. Many different samples like soap-water-farragoes, jelly-water-farragoes, agar-water-farragoes, soap-ethanol-farragoes and more are, for the project, examined in regard of their physical properties to find the best substitute fluid. The samples are examined at the rotational viscometer for viscosity at various shear rates and then compared with the viscosity values of liquid manure.

  19. Substitute fluid examinations for liquid manure

    Directory of Open Access Journals (Sweden)

    Schrader Kevin

    2017-01-01

    Full Text Available For the farming industry it is essential to use liquid manure as natural fertilizer. Through new agricultural regulation 2015 in Germany the industry must develop new liquid manure spreader systems because the ammonia and methane emission are limited. In a research project the University of Applied Sciences Zwickau and some other industry partners will develop such a new innovative liquid manure spreader. The new liquid manure spreader should use pulsating air to distribute the liquid manure exactly. The pulsating air, which flows through the pipelines, should be analysed at a test station. For examinations at this test station it is important to find another substitute fluid because liquid manure smells strong, is not transparent and is also not homogeneous enough for scientific investigations. Furthermore it is important to ensure that the substitute fluid is, like liquid manure, a non-Newtonian fluid. The substitute fluid must be a shear-thinning substance - this means the viscosity decrease at higher shear rate. Many different samples like soap-water-farragoes, jelly-water-farragoes, agar-water-farragoes, soap-ethanol-farragoes and more are, for the project, examined in regard of their physical properties to find the best substitute fluid. The samples are examined at the rotational viscometer for viscosity at various shear rates and then compared with the viscosity values of liquid manure.

  20. Consumers' perception of generic substitution in Iran.

    Science.gov (United States)

    Yousefi, Nazila; Mehralian, Gholamhossein; Peiravian, Farzad; NourMohammadi, Samaneh

    2015-06-01

    The growth of pharmaceutical expenditure and patients' out of pocket has motivated policy makers to encourage patients to substitution of brands medicines with their generic alternatives called generic substitution. As the patients are final decision makers to accept generic substitution, the aim of this study is to evaluate the patient perception about generic medicines and underlying factors which can promote the generic acceptance. The study was done in community pharmacies in Tehran, the capital city of Iran. A cross-sectional descriptive study inviting people purchasing their drug at community pharmacies were per-formed using a self-administrated anonymous questionnaire (N=1309). Besides the demographic section, 16 items of developed questionnaire were categorized to five main factors including: patients' perception about efficiency, safety and cost of generic medicines, patient trust on physicians and pharmacists' advice. Findings of completed questionnaires showed among the aforementioned factors the physician has the first priority to encourage patients to use of generics medicines which followed respectively by pharmacist's role, cost of medicines, efficacy, and safety concerns. In conclusion, the trust of Iranian's society on the physicians and pharmacists advice would create a credible opportunity to reduce pharmaceutical expenditures as well as patients' out of pocket by promotion of generic substitution.

  1. Dodecatungstocobaltate and Sn (IV)-Substituted Polyoxometalate ...

    African Journals Online (AJOL)

    NICO

    because of their unique reactivity, which depends on the compo- sition and structure of the active sites.9 Substituted ... molybdate and sodium tungstate were obtained from Merck and Co(OAc)2.4H2O and potassium persulfate ... The sodium salt was then converted to the potassium salt by treatment with potassium chloride.

  2. chromic transitions in phenyl-substituted polythiophenes

    African Journals Online (AJOL)

    The solvatochromic and thermochromic behaviours of phenyl-substituted polythiophenes were studied. The pristine polymers, upon dissolution in chloroform, exhibited blue-shifted absorption. The solid films of the polymers showed significant blue-shifted as well as red-shifted absorptions when heated. While the addition of ...

  3. Complexity Measure Revisited: A New Algorithm for Classifying Cardiac Arrhythmias

    Science.gov (United States)

    2001-10-25

    Complexity Measure Revisited: A New Algorithm for Classifying Cardiac Arrhythmias Contract Number Grant Number Program Element Number Author(s) Project...to set-up the acquisition and processing characteristics of ECG signal. REFERENCES [1] Special Issue on Electrical Therapy of Cardiac Arrhythmias , 3URFHHGLQJV...JM Jenkins, LA DiCarlo. “Detection and Identification of Cardiac Arrhythmias Using an adaptive, Linear-Predictive Filter”, ,((( &RPSXWHUV LQ

  4. Quark matter revisited with non-extensive MIT bag model

    Energy Technology Data Exchange (ETDEWEB)

    Cardoso, Pedro H.G.; Nunes da Silva, Tiago; Menezes, Debora P. [Universidade Federal de Santa Catarina, Departamento de Fisica, CFM, Florianopolis (Brazil); Deppman, Airton [Instituto de Fisica da Universidade de Sao Paulo, Sao Paulo (Brazil)

    2017-10-15

    In this work we revisit the MIT bag model to describe quark matter within both the usual Fermi-Dirac and the Tsallis statistics. We verify the effects of the non-additivity of the latter by analysing two different pictures: the first order phase transition of the QCD phase diagram and stellar matter properties. While the QCD phase diagram is visually affected by the Tsallis statistics, the resulting effects on quark star macroscopic properties are barely noticed. (orig.)

  5. Serotype-specific mortality from invasive Streptococcus pneumoniae disease revisited

    DEFF Research Database (Denmark)

    Martens, Pernille; Worm, Signe Westring; Lundgren, Bettina

    2004-01-01

    Serotype-specific mortality from invasive Streptococcus pneumoniae disease revisited.Martens P, Worm SW, Lundgren B, Konradsen HB, Benfield T. Department of Infectious Diseases 144, Hvidovre University Hospital, DK-2650 Hvidovre, Denmark. pernillemartens@yahoo.com BACKGROUND: Invasive infection...... with Streptococcus pneumoniae (pneumococci) causes significant morbidity and mortality. Case series and experimental data have shown that the capsular serotype is involved in the pathogenesis and a determinant of disease outcome. METHODS: Retrospective review of 464 cases of invasive disease among adults diagnosed...

  6. Deja vu: The Unified Command Plan of the Future Revisited

    Science.gov (United States)

    2011-05-19

    Approved for Public Release; Distribution is Unlimited Déjà vu : The Unified Command Plan of the Future Revisited A Monograph by Lieutenant...DD-MM-YYYY) 19-05-2011 2. REPORT TYPE Monograph 3. DATES COVERED (From - To) JUL 2010 – MAY 2011 4. TITLE AND SUBTITLE Déjà vu : The Unified...i SCHOOL OF ADVANCED MILITARY STUDIES MONOGRAPH APPROVAL Lieutenant Colonel Edward Francis Martignetti Title of Monograph: Déjà vu : The Unified

  7. Brand extensions: brand concept congruency and feedback effects revisited

    OpenAIRE

    Thorbjørnsen, Helge

    2005-01-01

    -This is the author's version of the article:"Brand extensions: brand concept congruency and feedback effects revisited" Journal of Product & Brand Management, Vol. 14 Iss: 4, pp.250 - 257, Abstract Purpose – The aim of this research is to examine the effects of congruent and incongruent brand concept extensions on consumer attitudes towards the extended product and feedback effects on the parent brand. Moreover, brand familiarity is proposed as an important mo...

  8. Revisiting the Response Mechanism of Polymeric Membrane Based Heparin Electrodes

    OpenAIRE

    Bell, Andrea K.; Höfler, Lajos; Meyerhoff, Mark E.

    2011-01-01

    Potentiometric membrane electrodes that respond to heparin and other polyanions were introduced in the early 1990s. Herein, the mechanism of polymer membrane electrode type heparin sensors is revisited. The extraction/diffusion of heparin is studied via both potentiometric and impedance spectroscopic techniques using a pre-fractionated heparin preparation that contains polyanionic species > 10000 Daltons. The reversal in EMF response using this heparin preparation indicates diffusion of highe...

  9. Dispute Resolution and Technology: Revisiting the Justification of Conflict Management

    OpenAIRE

    Koulu, Riikka

    2016-01-01

    This study, Dispute Resolution and Technology: Revisiting the Justification of Conflict Management, belongs to the fields of procedural law, legal theory and law and technology studies. In this study the changes in dispute resolution caused by technology are evaluated. The overarching research question of this study is how does implementing technology to dispute resolution challenge the justification of law as a legitimised mode of violence? Before answering such an abstract research question...

  10. Place attachment and social legitimacy: Revisiting the sustainable entrepreneurship journey

    OpenAIRE

    Kibler, Ewald; Fink, Matthias; Lang, R.; Munoz, P.

    2015-01-01

    This paper revisits the sustainable entrepreneurship journey by introducing a ‘place- based’ sustainable venture path model. We suggest that distinguishing between emo- tional (‘caring about the place’) and instrumental (‘using the place’) place attachment of sustainable entrepreneurs deepens our understanding of how place-based challenges of sustainable venture legitimacy are managed over time. We conclude with avenues for future sustainable entrepreneurship research.

  11. Indoor air and human health revisited: A recent IAQ symposium

    Energy Technology Data Exchange (ETDEWEB)

    Gammage, R.B.

    1994-12-31

    Indoor Air and Human Health Revisited was a speciality symposium examining the scientific underpinnings of sensory and sensitivity effects, allergy and respiratory disease, neurotoxicity and cancer. An organizing committee selected four persons to chain the sessions and invite experts to give state-of-the-art presentations that will be published as a book. A summary of the presentations is made and some critical issues identified.

  12. Comparative Ab-Initio Study of Substituted Norbornadiene-Quadricyclane Compounds for Solar Thermal Storage.

    Science.gov (United States)

    Kuisma, Mikael J; Lundin, Angelica M; Moth-Poulsen, Kasper; Hyldgaard, Per; Erhart, Paul

    2016-02-25

    Molecular photoswitches that are capable of storing solar energy, so-called molecular solar thermal storage systems, are interesting candidates for future renewable energy applications. In this context, substituted norbornadiene-quadricyclane systems have received renewed interest due to recent advances in their synthesis. The optical, thermodynamic, and kinetic properties of these systems can vary dramatically depending on the chosen substituents. The molecular design of optimal compounds therefore requires a detailed understanding of the effect of individual substituents as well as their interplay. Here, we model absorption spectra, potential energy storage, and thermal barriers for back-conversion of several substituted systems using both single-reference (density functional theory using PBE, B3LYP, CAM-B3LYP, M06, M06-2x, and M06-L functionals as well as MP2 calculations) and multireference methods (complete active space techniques). Already the diaryl substituted compound displays a strong red-shift compared to the unsubstituted system, which is shown to result from the extension of the conjugated π-system upon substitution. Using specific donor/acceptor groups gives rise to a further albeit relatively smaller red-shift. The calculated storage energy is found to be rather insensitive to the specific substituents, although solvent effects are likely to be important and require further study. The barrier for thermal back-conversion exhibits strong multireference character and as a result is noticeably correlated with the red-shift. Two possible reaction paths for the thermal back-conversion of diaryl substituted quadricyclane are identified and it is shown that among the compounds considered the path via the acceptor side is systematically favored. Finally, the present study establishes the basis for high-throughput screening of norbornadiene-quadricyclane compounds as it provides guidelines for the level of accuracy that can be expected for key properties from

  13. Inversion of substrate stereoselectivity of horse liver alcohol dehydrogenase by substitutions of Ser-48 and Phe-93

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Keehyuk; Plapp, Bryce V.

    2017-10-01

    The substrate specificities of alcohol dehydrogenases (ADH) are of continuing interest for understanding the physiological functions of these enzymes. Ser-48 and Phe-93 have been identified as important residues in the substrate binding sites of ADHs, but more comprehensive structural and kinetic studies are required. The S48T substitution in horse ADH1E has small effects on kinetic constants and catalytic efficiency (V/Km) with ethanol, but decreases activity with benzyl alcohol and affinity for 2,2,2-trifluoroethanol (TFE) and 2,3,4,5,6-pentafluorobenzyl alcohol (PFB). Nevertheless, atomic resolution crystal structures of the S48T enzyme complexed with NAD+ and TFE or PFB are very similar to the structures for the wild-type enzyme. (The S48A substitution greatly diminishes catalytic activity.) The F93A substitution significantly decreases catalytic efficiency (V/Km) for ethanol and acetaldehyde while increasing activity for larger secondary alcohols and the enantioselectivity for the R-isomer relative to the S-isomer of 2-alcohols. The doubly substituted S48T/F93A enzyme has kinetic constants for primary and secondary alcohols similar to those for the F93A enzyme, but the effect of the S48T substitution is to decrease V/Km for (S)-2-alcohols without changing V/Km for (R)-2-alcohols. Thus, the S48T/F93A substitutions invert the enantioselectivity for alcohol oxidation, increasing the R/S ratio by 10, 590, and 200-fold for 2-butanol, 2-octanol, and sec-phenethyl alcohol, respectively. Transient kinetic studies and simulations of the ordered bi bi mechanism for the oxidation of the 2-butanols by the S48T/F93A ADH show that the rate of hydride transfer is increased about 7-fold for both isomers (relative to wild-type enzyme) and that the inversion of enantioselectivity is due to more productive binding for (R)-2-butanol than for (S)-2-butanol in the ternary complex. Molecular modeling suggests that both of the sec-phenethyl alcohols could bind to the enzyme and that

  14. Inversion of substrate stereoselectivity of horse liver alcohol dehydrogenase by substitutions of Ser-48 and Phe-93.

    Science.gov (United States)

    Kim, Keehyuk; Plapp, Bryce V

    2017-10-01

    The substrate specificities of alcohol dehydrogenases (ADH) are of continuing interest for understanding the physiological functions of these enzymes. Ser-48 and Phe-93 have been identified as important residues in the substrate binding sites of ADHs, but more comprehensive structural and kinetic studies are required. The S48T substitution in horse ADH1E has small effects on kinetic constants and catalytic efficiency (V/Km) with ethanol, but decreases activity with benzyl alcohol and affinity for 2,2,2-trifluoroethanol (TFE) and 2,3,4,5,6-pentafluorobenzyl alcohol (PFB). Nevertheless, atomic resolution crystal structures of the S48T enzyme complexed with NAD+ and TFE or PFB are very similar to the structures for the wild-type enzyme. (The S48A substitution greatly diminishes catalytic activity.) The F93A substitution significantly decreases catalytic efficiency (V/Km) for ethanol and acetaldehyde while increasing activity for larger secondary alcohols and the enantioselectivity for the R-isomer relative to the S-isomer of 2-alcohols. The doubly substituted S48T/F93A enzyme has kinetic constants for primary and secondary alcohols similar to those for the F93A enzyme, but the effect of the S48T substitution is to decrease V/Km for (S)-2-alcohols without changing V/Km for (R)-2-alcohols. Thus, the S48T/F93A substitutions invert the enantioselectivity for alcohol oxidation, increasing the R/S ratio by 10, 590, and 200-fold for 2-butanol, 2-octanol, and sec-phenethyl alcohol, respectively. Transient kinetic studies and simulations of the ordered bi bi mechanism for the oxidation of the 2-butanols by the S48T/F93A ADH show that the rate of hydride transfer is increased about 7-fold for both isomers (relative to wild-type enzyme) and that the inversion of enantioselectivity is due to more productive binding for (R)-2-butanol than for (S)-2-butanol in the ternary complex. Molecular modeling suggests that both of the sec-phenethyl alcohols could bind to the enzyme and that

  15. Kinetics and Mechanism of the Anilinolysis of Aryl Ethyl Isothiocyanophosphates in Acetonitrile

    Energy Technology Data Exchange (ETDEWEB)

    Barai, Hasi Rani; Adhikary, Keshab Kumar; Lee, Hai Whang [Inha Univ., Incheon (Korea, Republic of)

    2013-06-15

    The nucleophilic substitution reactions of Y-aryl ethyl isothiocyanophosphates with substituted X-anilines and deuterated X-anilines were investigated kinetically in acetonitrile at 75.0 .deg. C. The free energy relationships with X in the nucleophiles exhibited biphasic concave downwards with a break point at X = H. A stepwise mechanism with rate-limiting bond formation for strongly basic anilines and with rate-limiting bond breaking for weakly basic anilines is proposed based on the negative and positive ρ{sub XY} values, respectively. The deuterium kinetic isotope effects (DKIEs; k{sub H}/k{sub D}) changed gradually from primary normal with strongly basic anilines, via primary normal and secondary inverse with aniline, to secondary inverse with weakly basic anilines. The primary normal and secondary inverse DKIEs were rationalized by frontside attack involving hydrogen bonded, four-center-type TSf and backside attack involving in-line-type TSb, respectively.

  16. Modeling the kinetics of vulcanization polydienes

    National Research Council Canada - National Science Library

    V. I. Molchanov; O. V. Karmanova; S. G. Tikhomirov

    2013-01-01

    A model of vulcanization kinetics, which allows describing the kinetic curves of any form and on the basis of economical laboratory experiment analytically evaluate the kinetics of isothermal curing was proposed...

  17. A kinetic theory treatment of heat transfer in plane Poiseuille flow with uniform pressure

    Science.gov (United States)

    Bahrami, Parviz A.

    1992-01-01

    Plane compressible Poiseuille flow with uniform pressure (Couette flow with stationary boundaries) is revisited where the Lees two-steam method with the Enskog equation of change is applied. Single particle velocity distribution functions are chosen, which preserve the essential physical features of this flow with arbitrary but uniform plate temperatures and gas pressure. Lower moments are shown to lead to expressions for the parameter functions, molecular number densities, and temperatures which are entirely in agreement with those obtained in the analysis of Lees for compressible plane Couette flow in the limit of low Mach number and vanishing mean gas velocity. Important simplifications result, which are helpful in gaining insight into the power of kinetic theory in fluid mechanics. The temperature distribution, heat flux, as well as density, are completely determined for the whole range of Knudson numbers from free molecular flow to the continuum regime, when the pressure level is specified.

  18. Inhibition by Avibactam and Clavulanate of the β-Lactamases KPC-2 and CTX-M-15 Harboring the Substitution N132G in the Conserved SDN Motif.

    Science.gov (United States)

    Ourghanlian, Clément; Soroka, Daria; Arthur, Michel

    2017-03-01

    The substitution N 132 G in the SDN motif of class A β-lactamases from rapidly growing mycobacteria was previously shown to impair their inhibition by avibactam but to improve the stability of acyl-enzymes formed with clavulanate. The same substitution was introduced in KPC-2 and CTX-M-15 to assess its impact on β-lactamases from Enterobacteriaceae and evaluate whether it may lead to resistance to the ceftazidime-avibactam combination. Kinetic parameters for the inhibition of the β-lactamases by avibactam and clavulanate were determined by spectrophotometry using nitrocefin as the substrate. The substitution N 132 G impaired (>1,000-fold) the efficacy of carbamylation of KPC-2 and CTX-M-15 by avibactam. The substitution improved the inhibition of KPC-2 by clavulanate due to reduced deacylation, whereas the presence or absence of N 132 G resulted in the inhibition of CTX-M-15 by clavulanate. The hydrolysis of amoxicillin and nitrocefin by KPC-2 and CTX-M-15 was moderately affected by the substitution N 132 G, but that of ceftazidime, ceftaroline, and aztreonam was drastically reduced. Isogenic strains producing KPC-2 and CTX-M-15 were constructed to assess the impact of the substitution N 132 G on the antibacterial activities of β-lactam-inhibitor combinations. For amoxicillin, the substitution resulted in resistance and susceptibility for avibactam and clavulanate, respectively. For ceftazidime, ceftaroline, and aztreonam, the negative impact of the substitution on β-lactamase activity prevented resistance to the β-lactam-avibactam combinations. In conclusion, the N 132 G substitution has profound effects on the substrate and inhibition profiles of class A β-lactamases, which are largely conserved in distantly related enzymes. Fortunately, the substitution does not lead to resistance to the ceftazidime-avibactam combination. Copyright © 2017 American Society for Microbiology.

  19. Inhibition by Avibactam and Clavulanate of the β-Lactamases KPC-2 and CTX-M-15 Harboring the Substitution N132G in the Conserved SDN Motif

    Science.gov (United States)

    Ourghanlian, Clément; Soroka, Daria

    2017-01-01

    ABSTRACT The substitution N132G in the SDN motif of class A β-lactamases from rapidly growing mycobacteria was previously shown to impair their inhibition by avibactam but to improve the stability of acyl-enzymes formed with clavulanate. The same substitution was introduced in KPC-2 and CTX-M-15 to assess its impact on β-lactamases from Enterobacteriaceae and evaluate whether it may lead to resistance to the ceftazidime-avibactam combination. Kinetic parameters for the inhibition of the β-lactamases by avibactam and clavulanate were determined by spectrophotometry using nitrocefin as the substrate. The substitution N132G impaired (>1,000-fold) the efficacy of carbamylation of KPC-2 and CTX-M-15 by avibactam. The substitution improved the inhibition of KPC-2 by clavulanate due to reduced deacylation, whereas the presence or absence of N132G resulted in the inhibition of CTX-M-15 by clavulanate. The hydrolysis of amoxicillin and nitrocefin by KPC-2 and CTX-M-15 was moderately affected by the substitution N132G, but that of ceftazidime, ceftaroline, and aztreonam was drastically reduced. Isogenic strains producing KPC-2 and CTX-M-15 were constructed to assess the impact of the substitution N132G on the antibacterial activities of β-lactam–inhibitor combinations. For amoxicillin, the substitution resulted in resistance and susceptibility for avibactam and clavulanate, respectively. For ceftazidime, ceftaroline, and aztreonam, the negative impact of the substitution on β-lactamase activity prevented resistance to the β-lactam–avibactam combinations. In conclusion, the N132G substitution has profound effects on the substrate and inhibition profiles of class A β-lactamases, which are largely conserved in distantly related enzymes. Fortunately, the substitution does not lead to resistance to the ceftazidime-avibactam combination. PMID:28069651

  20. Substitution treatment for opioid addicts in Germany

    Directory of Open Access Journals (Sweden)

    Gerlach Ralf

    2007-02-01

    Full Text Available Abstract Background After a long and controversial debate methadone maintenance treatment (MMT was first introduced in Germany in 1987. The number of patients in MMT – first low because of strict admission criteria – increased considerably since the 1990s up to some 65,000 at the end of 2006. In Germany each general practitioner (GP, who has completed an additional training in addiction medicine, is allowed to prescribe substitution drugs to opioid dependent patients. Currently 2,700 GPs prescribe substitution drugs. Psychosocial care should be made available to all MMT patients. Results The results of research studies and practical experiences clearly indicate that patients benefit substantially from MMT with improvements in physical and psychological health. MMT proves successful in attaining high retention rates (65 % to 85 % in the first years, up to 50 % after more than seven years and plays a major role in accessing and maintaining ongoing medical treatment for HIV and hepatitis. MMT is also seen as a vital factor in the process of social re-integration and it contributes to the reduction of drug related harms such as mortality and morbidity and to the prevention of infectious diseases. Some 10 % of MMT patients become drug-free in the long run. Methadone is the most commonly prescribed substitution medication in Germany, although buprenorphine is attaining rising importance. Access to MMT in rural areas is very patchy and still constitutes a problem. There are only few employment opportunities for patients participating in MMT, although regular employment is considered unanimously as a positive factor of treatment success. Substitution treatment in German prisons is heterogeneous in access and treatment modalities. Access is very patchy and the number of inmates in treatment is limited. Nevertheless, substitution treatment plays a substantial part in the health care system provided to drug users in Germany. Conclusion In Germany, a

  1. Substitution treatment for opioid addicts in Germany

    Science.gov (United States)

    Michels, Ingo Ilja; Stöver, Heino; Gerlach, Ralf

    2007-01-01

    Background After a long and controversial debate methadone maintenance treatment (MMT) was first introduced in Germany in 1987. The number of patients in MMT – first low because of strict admission criteria – increased considerably since the 1990s up to some 65,000 at the end of 2006. In Germany each general practitioner (GP), who has completed an additional training in addiction medicine, is allowed to prescribe substitution drugs to opioid dependent patients. Currently 2,700 GPs prescribe substitution drugs. Psychosocial care should be made available to all MMT patients. Results The results of research studies and practical experiences clearly indicate that patients benefit substantially from MMT with improvements in physical and psychological health. MMT proves successful in attaining high retention rates (65 % to 85 % in the first years, up to 50 % after more than seven years) and plays a major role in accessing and maintaining ongoing medical treatment for HIV and hepatitis. MMT is also seen as a vital factor in the process of social re-integration and it contributes to the reduction of drug related harms such as mortality and morbidity and to the prevention of infectious diseases. Some 10 % of MMT patients become drug-free in the long run. Methadone is the most commonly prescribed substitution medication in Germany, although buprenorphine is attaining rising importance. Access to MMT in rural areas is very patchy and still constitutes a problem. There are only few employment opportunities for patients participating in MMT, although regular employment is considered unanimously as a positive factor of treatment success. Substitution treatment in German prisons is heterogeneous in access and treatment modalities. Access is very patchy and the number of inmates in treatment is limited. Nevertheless, substitution treatment plays a substantial part in the health care system provided to drug users in Germany. Conclusion In Germany, a history of substitution

  2. Kinetics of self-interstitials reactions in p-type silicon irradiated with alpha particles

    Energy Technology Data Exchange (ETDEWEB)

    Makarenko, L.F., E-mail: makarenko@bsu.by [Department of Applied Mathematics and Computer Science, Belarusian State University, Independence Ave. 4, 220030 Minsk (Belarus); Moll, M. [CERN, Geneva (Switzerland); Evans-Freeman, J.H. [University of Canterbury, Christchurch (New Zealand); Lastovski, S.B.; Murin, L.I.; Korshunov, F.P. [Scientific-Practical Materials Research Centre of NAS of Belarus, Minsk (Belarus)

    2012-08-01

    New findings on the self-interstitial migration in p-type silicon are presented. They are based on experimental studies of the formation kinetics of defects related to interstitial carbon after irradiation with alpha particles. The main parameters characterizing the interaction rate of silicon self-interstitials with substitutional carbon atoms have been determined. A preliminary interpretation of the experimental data is given. The interpretation takes into account different diffusivities of self-interstitials in their singly and doubly ionized states.

  3. Fundamental studies on kinetic isotope effect (KIE) of hydrogen isotope fractionation in natural gas systems

    Science.gov (United States)

    Ni, Y.; Ma, Q.; Ellis, G.S.; Dai, J.; Katz, B.; Zhang, S.; Tang, Y.

    2011-01-01

    Based on quantum chemistry calculations for normal octane homolytic cracking, a kinetic hydrogen isotope fractionation model for methane, ethane, and propane formation is proposed. The activation energy differences between D-substitute and non-substituted methane, ethane, and propane are 318.6, 281.7, and 280.2cal/mol, respectively. In order to determine the effect of the entropy contribution for hydrogen isotopic substitution, a transition state for ethane bond rupture was determined based on density function theory (DFT) calculations. The kinetic isotope effect (KIE) associated with bond rupture in D and H substituted ethane results in a frequency factor ratio of 1.07. Based on the proposed mathematical model of hydrogen isotope fractionation, one can potentially quantify natural gas thermal maturity from measured hydrogen isotope values. Calculated gas maturity values determined by the proposed mathematical model using ??D values in ethane from several basins in the world are in close agreement with similar predictions based on the ??13C composition of ethane. However, gas maturity values calculated from field data of methane and propane using both hydrogen and carbon kinetic isotopic models do not agree as closely. It is possible that ??D values in methane may be affected by microbial mixing and that propane values might be more susceptible to hydrogen exchange with water or to analytical errors. Although the model used in this study is quite preliminary, the results demonstrate that kinetic isotope fractionation effects in hydrogen may be useful in quantitative models of natural gas generation, and that ??D values in ethane might be more suitable for modeling than comparable values in methane and propane. ?? 2011 Elsevier Ltd.

  4. Di-interstitial defect in silicon revisited

    Energy Technology Data Exchange (ETDEWEB)

    Londos, C. A.; Antonaras, G. [Solid State Section, Physics Department, University of Athens, Panepistimiopolis, Zografos, 157 84 Athens (Greece); Chroneos, A. [Engineering and Innovation, The Open University, Milton Keynes MK7 6AA (United Kingdom); Department of Materials, Imperial College London, London SW7 2BP (United Kingdom)

    2013-11-21

    Infrared spectroscopy was used to study the defect spectrum of Cz-Si samples following fast neutron irradiation. We mainly focus on the band at 533 cm{sup −1}, which disappears from the spectra at ∼170 °C, exhibiting similar thermal stability with the Si-P6 electron paramagnetic resonance (EPR) spectrum previously correlated with the di-interstitial defect. The suggested structural model of this defect comprises of two self-interstitial atoms located symmetrically around a lattice site Si atom. The band anneals out following a first-order kinetics with an activation energy of 0.88 ± 0.3 eV. This value does not deviate considerably from previously quoted experimental and theoretical values for the di-interstitial defect. The present results indicate that the 533 cm{sup −1} IR band originates from the same structure as that of the Si-P6 EPR spectrum.

  5. [The substitution effect of leadership substitutes for transformational leadership in nursing organization].

    Science.gov (United States)

    Kim, Jeong-Hee

    2006-04-01

    This paper was conducted to examine the effects of transformational leadership behaviors, within the substitutes for leadership model (Kerr & Jermier, 1978). Data was collected from 181 staff nurses in 3 general hospitals, with self-reporting questionnaires (MLQ developed by Bass, rd-SLS developed by Podsakoff, et al., and MSQ developed by Weiss, et al.). Descriptive statistics, factor analysis, Cronbach's alpha and moderated regression analysis were used. 1) The transformational leader behaviors and substitutes for leadership each had correlations with job satisfaction. 2) The total amount of variance accounted for by the substitutes for leadership was substantially greater than by the transformational leadership behaviors. 3) Few of the substitutes variables moderated the relationships between the transformational leader behaviors and job satisfaction in a manner consistent with that specified by Howell, Dorfman, and Kerr (1986). The finding of this study suggest that leaders need to have a better understanding of those contextual variables that influence job satisfaction. Thus future research should focus attention on the moderating effects of substitutes, as well as the things that leaders can do to influence them. In addition, it may be good to examine the effects of substitutes on other criterion variables.

  6. Kinetics of Levoglucosenone Isomerization.

    Science.gov (United States)

    Krishna, Siddarth H; Walker, Theodore W; Dumesic, James A; Huber, George W

    2017-01-10

    We studied the acid-catalyzed isomerization of levoglucosenone (LGO) to 5-hydroxymethylfurfural (HMF) and developed a reaction kinetics model that describes the experimental data across a range of conditions (100-150 °C, 50-100 mm H2 SO4 , 50-150 mm LGO). LGO and its hydrated derivative exist in equilibrium under these reaction conditions. Thermal and catalytic degradation of HMF are the major sources of carbon loss. Within the range of conditions studied, higher temperatures and shorter reaction times favor the production of HMF. The yields of HMF and levulinic acid decrease monotonically as tetrahydrofuran is added to the aqueous solvent system, indicating that water plays a role in the LGO isomerization reaction. Initial-rate analyses show that HMF is produced solely from LGO rather than from the hydrated derivative of LGO. The results of this study are consistent with a mechanism for LGO isomerization that proceeds through hydration of the anhydro bridge, followed by ring rearrangement analogous to the isomerization of glucose to fructose. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Kinetic properties of cyanase.

    Science.gov (United States)

    Anderson, P M; Little, R M

    1986-04-08

    Cyanase is an inducible enzyme in Escherichia coli that catalyzes the hydrolysis of cyanate. Bicarbonate is required for activity, perhaps as a substrate, and the initial product of the reaction is carbamate, which spontaneously breaks down to ammonia and bicarbonate [Anderson, P. M. (1980) Biochemistry 19, 2882]. The purpose of this study was to characterize the kinetic properties of cyanase. Initial velocity studies showed that both cyanate and bicarbonate act as competitive substrate inhibitors. A number of monovalent anions act as inhibitors. Azide and acetate appear to act as competitive inhibitors with respect to cyanate and bicarbonate, respectively. Chloride, bromide, nitrate, nitrite, and formate also inhibit, apparently as the result of binding at either substrate site. Malonate and several other dicarboxylic dianions at very low concentrations display "slow-binding", reversible inhibition which can be prevented by saturating concentrations of either substrate. The results are consistent with a rapid equilibrium random mechanism in which bicarbonate acts as a substrate, bicarbonate and cyanate bind at adjacent anion-binding sites, and both substrates can bind at the other substrate anion binding site to give a dead-end complex.

  8. A density functional theory study of the structure of pure-silica and aluminium-substituted MFI nanosheets

    Energy Technology Data Exchange (ETDEWEB)

    Hernandez-Tamargo, Carlos E.; Roldan, Alberto [Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ (United Kingdom); School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT (United Kingdom); Leeuw, Nora H. de, E-mail: deleeuwn@cardiff.ac.uk [Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ (United Kingdom); School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT (United Kingdom)

    2016-05-15

    The layered MFI zeolite allows a straightforward hierarchization of the pore system which accelerates mass transfer and increases its lifetime as a catalyst. Here, we present a theoretical study of the structural features of the pure-silica and aluminium-substituted MFI nanosheets. We have analysed the effects of aluminium substitution on the vibrational properties of silanols as well as the features of protons as counter-ions. The formation of the two-dimensional system did not lead to appreciable distortions within the framework. Moreover, the effects on the structure due to the aluminium dopants were the same in both the bulk and the slab. The principal differences were related to the silanol groups that form hydrogen-bonds with neighbouring aluminium-substituted silanols, whereas intra-framework hydrogen-bonds increase the stability of aluminium-substituted silanols toward dehydration. Thus, we have complemented previous experimental and theoretical studies, showing the lamellar MFI zeolite to be a very stable material of high crystallinity regardless of its very thin structure. - Graphical abstract: The structure of MFI zeolite nanosheet was investigated using Density Functional Theory. The results showed no differences against the bulk-type material upon aluminium doping. The aluminium-substituted silanol dehydrates toward a more stable configuration composed by a water molecule adsorbed on a Lewis centre. - Highlights: • MFI nanosheets with variable thicknesses were characterised using DFT calculations. • The distortions in the nanosheets after Al substitution reproduced those of the bulk. • H-bonds were only observed between silanol groups when the Al substitution took place. • The kinetic of the Al-silanol dehydration is dependent on intra-framework H-bonds. • Lewis acids with adsorbed water are more stable than Al-silanols. • The proton accessibility was related to the framework O atom binding the proton.

  9. 19 CFR 351.521 - Import substitution subsidies. [Reserved

    Science.gov (United States)

    2010-04-01

    ... 19 Customs Duties 3 2010-04-01 2010-04-01 false Import substitution subsidies. 351.521 Section 351... COUNTERVAILING DUTIES Identification and Measurement of Countervailable Subsidies § 351.521 Import substitution subsidies. ...

  10. Reductive Heck Reactions of N-Methyl-substituted Tricyclic Imides

    OpenAIRE

    Gokce Goksu; Nuket Ocal; Dieter E. Kaufmann

    2010-01-01

    The palladium-catalyzed hydroarylation of N-methyl-substituted tricyclic imides was studied in order to find a new stereoselective access to a series of new exo-aryl(hetaryl)-substituted tricyclic N-methylimides.

  11. An Exploration of Substitutes for Leadership: Problems and Prospects

    National Research Council Canada - National Science Library

    Wu, Yu-Chi

    2010-01-01

    Despite the conceptual premise of Kerr and Jermier's (1978) substitutes for leadership model, there has been little evidence of empirical support when substitutes for leadership are modeled as interactions with leader behaviors...

  12. The Synthesis of Substituted Piperazine-cholesterol Conjugates for ...

    African Journals Online (AJOL)

    NICO

    , a set of cholesteryl derivatives, containing piperazines substituted with additional aromatic groups, were synthesized. (Table 2). These included the pyridine substituted piperazines. (6k) and (6l), as well as the 2-pyrimidine (6m). Of note is that.

  13. SUBSTITUTION OF CADMIUM CYANIDE ELECTROPLATING WITH ZINC CHLORIDE ELECTROPLATING

    Science.gov (United States)

    The study evaluated the zinc chloride electroplating process as a substitute for cadmium cyanide electroplating in the manufacture of industrial connectors and fittings at Aeroquip Corporation. The process substitution eliminates certain wastes, specifically cadmium and cyanide, ...

  14. Thomas Piketty’s capitalism revisited

    Directory of Open Access Journals (Sweden)

    Milovanović Milić

    2015-01-01

    Full Text Available Thomas Piketty’s international best selling Capital in the Twenty-First Century lays out his theory of a long-run rise in income inequality under capitalism. It is written as a manifesto urging reintegration of social sciences. A number of reviewers judged it on ideological grounds, labeling it either as a revolution in economic thinking, or dismissing it offhandedly. Piketty’s theory of rising inequality is based on the two Fundamental Laws of Capitalism, developed after the Solow growth model. However, this model is inconsistent with Piketty’s own characterization of modern capitalism. Moreover, his sole justification for the constant discrepancy between rate of return and rate of income growth (r > g is based on the high elasticity of substitution between capital and labor. However, that is just one factor that can have an influence on factor income shares. By failing to offer a consistent theory of rising inequality, his piece can hardly be considered as a useful founding stone for a new social science.

  15. Hydroxylation of p-substituted phenols by tyrosinase: Further insight into the mechanism of tyrosinase activity

    Energy Technology Data Exchange (ETDEWEB)

    Munoz-Munoz, Jose Luis [GENZ - Grupo de Investigacion Enzimologia, Departamento de Bioquimica y Biologia Molecular-A, Facultad de Biologia, Campus Internacional de Excelencia Campus Mare Nostrum, Universidad de Murcia, E-30100 Espinardo, Murcia (Spain); Berna, Jose [Grupo de Quimica Organica Sintetica, Departamento de Quimica Organica, Facultad de Quimica Campus Internacional de Excelencia Campus Mare Nostrum, Universidad de Murcia (Spain); Garcia-Molina, Maria del Mar; Garcia-Molina, Francisco [GENZ - Grupo de Investigacion Enzimologia, Departamento de Bioquimica y Biologia Molecular-A, Facultad de Biologia, Campus Internacional de Excelencia Campus Mare Nostrum, Universidad de Murcia, E-30100 Espinardo, Murcia (Spain); Garcia-Ruiz, Pedro Antonio [QCPAI - Grupo de Quimica de Carbohidratos, Polimeros y Aditivos Industriales, Departamento de Quimica Organica, Facultad de Quimica Campus Internacional de Excelencia Campus Mare Nostrum, Universidad de Murcia (Spain); Varon, Ramon [Departamento de Quimica-Fisica, Escuela de Ingenieros Industriales de Albacete, Universidad de Castilla la Mancha, Avda. Espana s/n. Campus Universitario, E-02071 Albacete (Spain); and others

    2012-07-27

    Highlights: Black-Right-Pointing-Pointer The action the copper complexes and tyrosinase on phenols is equivalent. Black-Right-Pointing-Pointer Isotope effect showed that nucleophilic attack to copper atom may be the slower step. Black-Right-Pointing-Pointer The value of {rho} (Hammett constant) supports an electrophilic aromatic substitution. Black-Right-Pointing-Pointer Data obtained in steady state pH 7 conditions support the mechanism of Scheme 1SM. -- Abstract: A study of the monophenolase activity of tyrosinase by measuring the steady state rate with a group of p-substituted monophenols provides the following kinetic information: k{sub cat}{sup m} and the Michaelis constant, K{sub M}{sup m}. Analysis of these data taking into account chemical shifts of the carbon atom supporting the hydroxyl group ({delta}) and {sigma}{sub p}{sup +}, enables a mechanism to be proposed for the transformation of monophenols into o-diphenols, in which the first step is a nucleophilic attack on the copper atom on the form E{sub ox} (attack of the oxygen of the hydroxyl group of C-1 on the copper atom) followed by an electrophilic attack (attack of the hydroperoxide group on the ortho position with respect to the hydroxyl group of the benzene ring, electrophilic aromatic substitution with a reaction constant {rho} of -1.75). These steps show the same dependency on the electronic effect of the substituent groups in C-4. Furthermore, a study of a solvent deuterium isotope effect on the oxidation of monophenols by tyrosinase points to an appreciable isotopic effect. In a proton inventory study with a series of p-substituted phenols, the representation of k{sub cat}{sup f{sub n}}/k{sub cat}{sup f{sub 0}} against n (atom fractions of deuterium), where k{sub cat}{sup f{sub n}} is the catalytic constant for a molar fraction of deuterium (n) and k{sub cat}{sup f{sub 0}} is the corresponding kinetic parameter in a water solution, was linear for all substrates. These results indicate that

  16. Preparation and characterization of selenite substituted hydroxyapatite

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Jun; Wang, Yanhua; Zhou, Lei [Advance Biomaterials and Tissue Engineering Center, Huazhong University of Science and Technology, Wuhan 430074 (China); Department of Biomedical Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China); Zhang, Shengmin, E-mail: caltary@gmail.com [Advance Biomaterials and Tissue Engineering Center, Huazhong University of Science and Technology, Wuhan 430074 (China); Department of Biomedical Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China); China-Korea Center for Biomaterials and Nano-biotechnology, Life Science Building, 1037 Luoyu Road, Wuhan 430074 (China)

    2013-01-01

    Selenite-substituted hydroxyapatite (Se-HA) with different Se/P ratios was synthesized by a co-precipitation method, using sodium selenite (Na{sub 2}SeO{sub 3}) as a Se source. Selenium has been incorporated into the hydroxyapatite lattice by partially replacing phosphate (PO{sub 4}{sup 3-}) groups with selenite (SeO{sub 3}{sup 2-}) groups. X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), and transmission electron microscopy (TEM) techniques reveal that substitutions of phosphate groups by selenite groups cause lower carbonate groups occupying at phosphate sites and change the lattice parameters of hydroxyapatite. The powders obtained are nano-crystalline hydroxyapatite when the Se/P ratios are not more than 0.1. The particle shape of Se-HA has not been altered compared with selenite-free hydroxyapatite but Se-incorporation reduces the crystallite size. The crystallinity was reduced as the Se/P ratios increased until amorphous phase (Se/P = 0.3) appeared in the Se-HA powder obtained, and then another crystal phase presented as calcium selenite hydrate (Se/P = 10). In addition, the sintering tests show that the Se-HA powders with the Se/P ratio of 0.1 have thermal stability at 900 Degree-Sign C for 2 h; hence they have great potential in the fabrication of bone repair scaffolds. - Highlights: Black-Right-Pointing-Pointer We investigate the Se/P ratio for the synthesis of selenium substituted HA. Black-Right-Pointing-Pointer Nano-crystalline HA structure is remained when Se/P ratio is below 0.1. Black-Right-Pointing-Pointer Calcium selenite hydrate forms when Se/P ratio is beyond 10. Black-Right-Pointing-Pointer Selenite substituted HA powders (Se/P < 0.1) are stable at 900 Degree-Sign C for 2 h.

  17. Synthesis of 2-azetidinones substituted quinoline derivative

    Directory of Open Access Journals (Sweden)

    Mashelkar Uday C.

    2013-01-01

    Full Text Available Acetanilide is converted into 2-chloro-3-formyl quinoline by reacting with DMF-POCl3 at 80-90ºC and then condensed with aromatic primary amines to give Schiff bases (3a-3c. These Schiff bases are then reacted with acid chlorides in the presence of base in toluene to give 1, 3, 4-substituted 2-azetidinones.

  18. GROUNDNUT SUBSTITUTE MEDIA FOR BACTERIOLOGICAL CULTURE

    OpenAIRE

    Saroj; Hemina; Praveg

    2014-01-01

    : BACKGROUND: In the developing countries manual methods are still used for the cultivation of the bacteria and many a times difficulties are involved in procuring suitable components for preparation of various nutrient media. The need has therefore arisen, to investigate the problem of exploitation of indigenous material such as groundnuts to substitute commercial preparations used in the various nutrient media for bacteriological culture. AIMS & OBJECTIVES: In the presen...

  19. Cell seeding chamber for bone graft substitutes

    OpenAIRE

    Hennig, J.; Schieker, Matthias; Seitz, H.

    2012-01-01

    There is an increasing demand for bone graft substitutes that are used as osteoconductive scaffolds in the treatment of bone defects and fractures. Achieving optimal bone regeneration requires initial cell seeding of the scaffolds prior to implantation. The cell seeding chamber is a closed assembly. It works like a sandglass. The position of the scaffold is between two reservoirs containing the fluid (e. g. blood). The fluid at the upper reservoir flows through the scaffold driven by gravity....

  20. Synthesis of 2-azetidinones substituted coumarin derivative

    Directory of Open Access Journals (Sweden)

    Jha Mukesh S.

    2012-01-01

    Full Text Available α-Naphthol is converted into 4-methylbenzo[h]chromen-2-one by reacting with ethyl acetoacetate in the presence of bismuth trichloride which is then oxidized to 2-oxo-2H-benzo[h]chromene-4-carbaldehyde and then condensed with aromatic primary amines to give Schiff bases (3a-3d. These Schiff bases are then reacted with acid chlorides in the presence of base in toluene to give 1, 3, 4-substituted 2-azetidinones.

  1. Kinetic ELISA in microfluidic channels

    National Research Council Canada - National Science Library

    Yanagisawa, Naoki; Dutta, Debashis

    2011-01-01

    In this article, we describe the kinetic ELISA of Blue Tongue and Epizootic Hemorrhagic Disease viral antibodies in microfluidic channels by monitoring the rate of generation of the enzyme reaction...

  2. Modelling Heart Rate Kinetics

    Science.gov (United States)

    Zakynthinaki, Maria S.

    2015-01-01

    The objective of the present study was to formulate a simple and at the same time effective mathematical model of heart rate kinetics in response to movement (exercise). Based on an existing model, a system of two coupled differential equations which give the rate of change of heart rate and the rate of change of exercise intensity is used. The modifications introduced to the existing model are justified and discussed in detail, while models of blood lactate accumulation in respect to time and exercise intensity are also presented. The main modification is that the proposed model has now only one parameter which reflects the overall cardiovascular condition of the individual. The time elapsed after the beginning of the exercise, the intensity of the exercise, as well as blood lactate are also taken into account. Application of the model provides information regarding the individual’s cardiovascular condition and is able to detect possible changes in it, across the data recording periods. To demonstrate examples of successful numerical fit of the model, constant intensity experimental heart rate data sets of two individuals have been selected and numerical optimization was implemented. In addition, numerical simulations provided predictions for various exercise intensities and various cardiovascular condition levels. The proposed model can serve as a powerful tool for a complete means of heart rate analysis, not only in exercise physiology (for efficiently designing training sessions for healthy subjects) but also in the areas of cardiovascular health and rehabilitation (including application in population groups for which direct heart rate recordings at intense exercises are not possible or not allowed, such as elderly or pregnant women). PMID:25876164

  3. 19 CFR 122.86 - Substitution of aircraft.

    Science.gov (United States)

    2010-04-01

    ... 19 Customs Duties 1 2010-04-01 2010-04-01 false Substitution of aircraft. 122.86 Section 122.86... Substitution of aircraft. (a) Application. The residue cargo procedure applies when an airline must substitute aircraft to reach a destination due to weather conditions or operational factors which prevent an aircraft...

  4. (N-Substituted-Anilino)-8-Hydroxyquinolines via Hartwig-Buchwald ...

    Indian Academy of Sciences (India)

    Abstract. Three novel 5-(N-substituted-anilino)-8-benzyloxyquinoline derivatives were efficiently synthe- sized via Hartwig–Buchwald amination reaction. The new 5-(N-substituted-anilino)-8-benzyloxyquinolines were reduced for 1–3 h to give the corresponding 5-(N-substituted-anilino)-8-hydroxyquinolines. Extending the.

  5. 17 CFR 10.32 - Substitution of parties.

    Science.gov (United States)

    2010-04-01

    ... 17 Commodity and Securities Exchanges 1 2010-04-01 2010-04-01 false Substitution of parties. 10.32... Parties and Limited Participation § 10.32 Substitution of parties. Upon motion and for good cause shown the Administrative Law Judge may order a substitution of parties. ...

  6. 40 CFR 721.1925 - Substituted carboheterocyclic butane tetracarboxylate (generic).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted carboheterocyclic butane... Specific Chemical Substances § 721.1925 Substituted carboheterocyclic butane tetracarboxylate (generic). (a... generically as substituted carboheterocyclic butane tetracarboxylate (PMNs P-90-440 and P-95-4) is subject to...

  7. 40 CFR 721.3435 - Butoxy-substituted ether alkane.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Butoxy-substituted ether alkane. 721... Substances § 721.3435 Butoxy-substituted ether alkane. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as butoxy-substituted ether alkane...

  8. 40 CFR 721.4365 - Substituted ethoxylated hydrocarbon (generic).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted ethoxylated hydrocarbon... Specific Chemical Substances § 721.4365 Substituted ethoxylated hydrocarbon (generic). (a) Chemical... as Substituted ethoxylated hydrocarbon (PMN P-99-0313) is subject to reporting under this section for...

  9. Substitute Addiction: A Concern for Researchers and Practitioners

    Science.gov (United States)

    Sussman, Steve; Black, David S.

    2008-01-01

    An understanding of the role of substitute addictions remains unclear. This article examines the range and possible reward functions of substitute addictions. We suggest that prevention education and treatment need to take into account substitute addictions as an influential aspect of recovery. Research is needed to better understand the…

  10. 40 CFR 203.5 - Suitable substitute decision.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 24 2010-07-01 2010-07-01 false Suitable substitute decision. 203.5... PROGRAMS LOW-NOISE-EMISSION PRODUCTS § 203.5 Suitable substitute decision. (a) If the Administrator... decide whether such product is a suitable substitute for any class or model or product being purchased by...

  11. 34 CFR 361.14 - Substitute State agency.

    Science.gov (United States)

    2010-07-01

    ... 34 Education 2 2010-07-01 2010-07-01 false Substitute State agency. 361.14 Section 361.14... Substitute State agency. (a) General provisions. (1) If the Secretary has withheld all funding from a State under § 361.11, the State may designate another agency to substitute for the designated State agency in...

  12. 12 CFR 27.6 - Substitute monitoring program.

    Science.gov (United States)

    2010-01-01

    ... 12 Banks and Banking 1 2010-01-01 2010-01-01 false Substitute monitoring program. 27.6 Section 27... DATA SYSTEM § 27.6 Substitute monitoring program. The recordkeeping provisions of § 27.3 constitute a substitute monitoring program as authorized under § 202.13(d) of Regulation B of the Federal Reserve Board...

  13. 40 CFR 721.2527 - Substituted diphenylazo dye (generic name).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted diphenylazo dye (generic... Specific Chemical Substances § 721.2527 Substituted diphenylazo dye (generic name). (a) Chemical substance... substituted diphenylazo dye (PMN P-95-514) is subject to reporting under this section for the significant new...

  14. 40 CFR 721.320 - Acrylamide-substituted epoxy.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Acrylamide-substituted epoxy. 721.320... Substances § 721.320 Acrylamide-substituted epoxy. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as acrylamide-substituted epoxy (PMN P-92-660...

  15. 40 CFR 721.4594 - Substituted azo metal complex dye.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted azo metal complex dye. 721... Substances § 721.4594 Substituted azo metal complex dye. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a substituted azo metal complex...

  16. 40 CFR 721.10118 - Substituted aryl acetonitrile (generic).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted aryl acetonitrile (generic... Specific Chemical Substances § 721.10118 Substituted aryl acetonitrile (generic). (a) Chemical substance... substituted aryl acetonitrile (PMN P-05-35) is subject to reporting under this section for the significant new...

  17. 40 CFR 721.3565 - Ethylenediamine, substituted, sodium salt.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Ethylenediamine, substituted, sodium... Specific Chemical Substances § 721.3565 Ethylenediamine, substituted, sodium salt. (a) Chemical substance... ethylenediamine, substituted, sodium salt (PMN P-97-328) is subject to reporting under this section for the...

  18. 21 CFR 184.1259 - Cocoa butter substitute.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Cocoa butter substitute. 184.1259 Section 184.1259... Listing of Specific Substances Affirmed as GRAS § 184.1259 Cocoa butter substitute. (a) The common or usual name for the triglyceride 1-palmitoyl-2-oleoyl-3-stearin is “cocoa butter substitute primarily...

  19. Interfuel substitution in the United States

    Energy Technology Data Exchange (ETDEWEB)

    Serletis, Apostolos; Vasetsky, Olexandr [Department of Economics, University of Calgary, Calgary, Alberta (Canada); Timilsina, Govinda R. [Development Research Group, The World Bank, 1818 H Street N.W., Washington, DC 20433 (United States)

    2010-05-15

    In this paper, we use the locally flexible translog functional form to investigate the demand for energy and interfuel substitution in the United States and to provide a comparison of our results with most of the existing empirical energy demand literature. Motivated by the widespread practice of ignoring theoretical regularity, we follow Barnett's (2002) suggestions and estimate the model subject to theoretical regularity, using methods developed by Diewert and Wales (1987) and Ryan and Wales (2000), in an attempt to produce inference consistent with neoclassical microeconomic theory. Moreover, we use the most recent data, published by the U.S. Energy Information Administration (EIA), and in addition to investigating interfuel substitution possibilities in total U.S. energy demand, we follow Serletis et al. (2009) and also examine interfuel substitution possibilities in energy demand by sector. Moreover, we test for weak separability, with the objective of discovering the structure of the functional form in total energy demand as well as energy demand by sector. (author)

  20. Intersection Type Systems and Explicit Substitutions Calculi

    Science.gov (United States)

    Ventura, Daniel Lima; Ayala-Rincón, Mauricio; Kamareddine, Fairouz

    The λ-calculus with de Bruijn indices, called λ dB , assembles each α-class of λ-terms into a unique term, using indices instead of variable names. Intersection types provide finitary type polymorphism satisfying important properties like principal typing, which allows the type system to include features such as data abstraction (modularity) and separate compilation. To be closer to computation and to simplify the formalisation of the atomic operations involved in β-contractions, several explicit substitution calculi were developed most of which are written with de Bruijn indices. Although untyped and simply types versions of explicit substitution calculi are well investigated, versions with more elaborate type systems (e.g., with intersection types) are not. In previous work, we presented a version for λ dB of an intersection type system originally introduced to characterise principal typings for β-normal forms and provided the characterisation for this version. In this work we introduce intersection type systems for two explicit substitution calculi: the λσ and the λs e . These type system are based on a type system for λ dB and satisfy the basic property of subject reduction, which guarantees the preservation of types during computations.

  1. Circular revisit orbits design for responsive mission over a single target

    Science.gov (United States)

    Li, Taibo; Xiang, Junhua; Wang, Zhaokui; Zhang, Yulin

    2016-10-01

    The responsive orbits play a key role in addressing the mission of Operationally Responsive Space (ORS) because of their capabilities. These capabilities are usually focused on supporting specific targets as opposed to providing global coverage. One subtype of responsive orbits is repeat coverage orbit which is nearly circular in most remote sensing applications. This paper deals with a special kind of repeating ground track orbit, referred to as circular revisit orbit. Different from traditional repeat coverage orbits, a satellite on circular revisit orbit can visit a target site at both the ascending and descending stages in one revisit cycle. This typology of trajectory allows a halving of the traditional revisit time and does a favor to get useful information for responsive applications. However the previous reported numerical methods in some references often cost lots of computation or fail to obtain such orbits. To overcome this difficulty, an analytical method to determine the existence conditions of the solutions to revisit orbits is presented in this paper. To this end, the mathematical model of circular revisit orbit is established under the central gravity model and the J2 perturbation. A constraint function of the circular revisit orbit is introduced, and the monotonicity of that function has been studied. The existent conditions and the number of such orbits are naturally worked out. Taking the launch cost into consideration, optimal design model of circular revisit orbit is established to achieve a best orbit which visits a target twice a day in the morning and in the afternoon respectively for several days. The result shows that it is effective to apply circular revisit orbits in responsive application such as reconnoiter of natural disaster.

  2. Revisiting the value of competition assays in folate receptor-mediated drug delivery.

    Science.gov (United States)

    Jones, Steven K; Sarkar, Anwesha; Feldmann, Daniel P; Hoffmann, Peter; Merkel, Olivia M

    2017-09-01

    Polymeric nanoparticles have been studied for gene and drug delivery. These nanoparticles can be modified to utilize a targeted delivery approach to selectively deliver their payload to specific cells, while avoiding unwanted delivery to healthy cells. One commonly over-expressed receptor which can be targeted by ligand-conjugated nanoparticles is the folate receptor alpha (FRα). The ability to target FRα remains a promising concept, and therefore, understanding the binding dynamics of the receptor with the ligand of the nanoparticle therapeutic can provide valuable insight. This manuscript focuses on the interaction between self-assembled nanoparticles decorated with a folic acid (FA) ligand and FRα. The nanoparticles consist of micelles formed with a FA conjugated triblock copolymer (PEI-g-PCL-b-PEG-FA) which condensed siRNA to form micelleplexes. By combining biological and biophysical approaches, this manuscript explores the binding kinetics and force of the targeted siRNA containing nanoparticles to FRα in comparison with free FA. We demonstrate via flow cytometry and atomic force microscopy that multivalent micelleplexes bind to FRα with a higher binding probability and binding force than monovalent FA. Furthermore, we revisited why competitive inhibition studies of binding of multivalent nanoparticles to their respective receptor are often reported in literature to be inconclusive evidence of effective receptor targeting. In conclusion, the results presented in this paper suggest that multivalent targeted nanoparticles display strong receptor binding that a monovalent ligand may not be able to compete with under in vitro conditions and that high concentrations of competing monovalent ligands can lead to measurement artifacts. Copyright © 2017 Elsevier Ltd. All rights reserved.

  3. The origin of life in geothermal hot springs: Darwin's warm little pond revisited

    Science.gov (United States)

    Deamer, D.

    2016-12-01

    The origin of life in geothermal hot springs: Darwin's warm little pond revisited David Deamer and Bruce Damer, Department of Biomolecular Engineering, University of California, Santa Cruz CA 95064 We are exploring ways in which mononucleotides can undergo polymerization and encapsulation in the presence of an organizing matrix (1, 2, 3). When mixtures of amphiphilic lipids and mononucleotides are exposed to cycles of dehydration and rehydration, the lipids concentrate and organize the monomers within multilamellar liquid-crystalline matrices that self-assemble in the dry state. The chemical potential driving the polymerization reaction is supplied by the anhydrous conditions in which water becomes a leaving group, with heat providing activation energy. Upon rehydration, the polymeric products are encapsulated in trillions of microscopic compartments. Each compartment is unique in its composition and contents, and can be considered to be an experiment in a natural version of combinatorial chemistry that would be ubiquitous in the prebiotic environment. There are specific thermodynamic and kinetic considerations required for this process to work which are related to cycles of evaporation and rehydration, ionic composition, salt concentration, pH and temperature. These conditions are present in hydrothermal fields associated with volcanic activity on today's Earth and can be compared with the range of possible conditions on Enceladus to estimate the probability that life can emerge on an icy world with a subsurface salty liquid ocean. 1. De Guzman V, Shenasa H, Vercoutere W, Deamer D (2014) Generation of oligonucleotides under hydrothermal conditions by non-enzymatic polymerization. J Mol Evol 78:251-262 2. Deamer D. 2012. Liquid crystalline nanostructures: organizing matrices for non-enzymatic nucleic acid polymerization. Chem Soc Rev. 41:5375-9. 3. Damer B, Deamer D. 2015. Coupled phases and combinatorial selection in fluctuating hydrothermal pools: a scenario to

  4. Revisiting Verhulst and Monod models: analysis of batch and fed-batch cultures.

    Science.gov (United States)

    Shirsat, Nishikant; Mohd, Avesh; Whelan, Jessica; English, Niall J; Glennon, Brian; Al-Rubeai, Mohamed

    2015-05-01

    The paper re-evaluates Verhulst and Monod models. It has been claimed that standard logistic equation cannot describe the decline phase of mammalian cells in batch and fed-batch cultures and in some cases it fails to fit somatic growth data. In the present work Verhulst, population-based mechanistic growth model was revisited to describe successfully viable cell density (VCD) in exponential and decline phases of batch and fed-batch cultures of three different CHO cell lines. Verhulst model constants, K, carrying capacity (VCD/ml or μg/ml) and r, intrinsic growth factor (h(-1)) have physical meaning and they are of biological significance. These two parameters together define the course of growth and productivity and therefore, they are valuable in optimisation of culture media, developing feeding strategies and selection of cell lines for productivity. The Verhulst growth model approach was extended to develop productivity models for batch and fed-batch cultures. All Verhulst models were validated against blind data (R(2) > 0.95). Critical examination of theoretical approaches concluded that Monod parameters have no physical meaning. Monod-hybrid (pseudo-mechanistic) batch models were validated against specific growth rates of respective bolus and continuous fed-batch cultures (R(2) ≈ 0.90). The reduced form of Monod-hybrid model CL/(KL + CL) describes specific growth rate during metabolic shift (R(2) ≈ 0.95). Verhulst substrate-based growth models compared favourably with Monod-hybrid models. Thus, experimental evidence implies that the constants in the Monod-hybrid model may not have physical meaning but they behave similarly to the biological constants in Michaelis-Menten enzyme kinetics, the basis of the Monod growth model.

  5. Crystallization Kinetics within a Generic Modelling Framework

    DEFF Research Database (Denmark)

    Meisler, Kresten Troelstrup; von Solms, Nicolas; Gernaey, Krist

    2013-01-01

    An existing generic modelling framework has been expanded with tools for kinetic model analysis. The analysis of kinetics is carried out within the framework where kinetic constitutive models are collected, analysed and utilized for the simulation of crystallization operations. A modelling...... procedure is proposed to gain the information of crystallization operation kinetic model analysis and utilize this for faster evaluation of crystallization operations....

  6. NEC violation in mimetic cosmology revisited

    Directory of Open Access Journals (Sweden)

    Anna Ijjas

    2016-09-01

    Full Text Available In the context of Einstein gravity, if the null energy condition (NEC is satisfied, the energy density in expanding space–times always decreases while in contracting space–times the energy density grows and the universe eventually collapses into a singularity. In particular, no non-singular bounce is possible. It is, though, an open question if this energy condition can be violated in a controlled way, i.e., without introducing pathologies, such as unstable negative-energy states or an imaginary speed of sound. In this letter, we will re-examine the claim that the recently proposed mimetic scenario can violate the NEC without pathologies. We show that mimetic cosmology is prone to gradient instabilities even in cases when the NEC is satisfied (except for trivial examples. Most interestingly, the source of the instability is always the Einstein–Hilbert term in the action. The matter stress-energy component does not contribute spatial gradient terms but instead makes the problematic curvature modes dynamical. We also show that mimetic cosmology can be understood as a singular limit of known, well-behaved theories involving higher-derivative kinetic terms and discuss ways of removing the instability.

  7. Dynamical Properties of Internal Shocks Revisited

    Energy Technology Data Exchange (ETDEWEB)

    Pe’er, Asaf; Long, Killian [Physics Department, University College Cork, Cork (Ireland); Casella, Piergiorgio [INAF, Osservatorio Astronomico di Roma, Via Frascati 33, I-00078 Monteporzio Catone (Italy)

    2017-09-01

    Internal shocks between propagating plasma shells, originally ejected at different times with different velocities, are believed to play a major role in dissipating the kinetic energy, thereby explaining the observed light curves and spectra in a large range of transient objects. Even if initially the colliding plasmas are cold, following the first collision, the plasma shells are substantially heated, implying that in a scenario of multiple collisions, most collisions take place between plasmas of non-zero temperatures. Here, we calculate the dynamical properties of plasmas resulting from a collision between arbitrarily hot plasma shells, moving at arbitrary speeds. We provide simple analytical expressions valid for both ultrarelativistic and Newtonian velocities for both hot and cold plasmas. We derive the minimum criteria required for the formation of the two-shock wave system, and show that in the relativistic limit, the minimum Lorentz factor is proportional to the square root of the ratio of the initial plasmas enthalpies. We provide basic scaling laws of synchrotron emission from both the forward and reverse-shock waves, and show how these can be used to deduce the properties of the colliding shells. Finally, we discuss the implications of these results in the study of several astronomical transients, such as X-ray binaries, radio-loud quasars, and gamma-ray bursts.

  8. A practical method of predicting client revisit intention in a hospital setting.

    Science.gov (United States)

    Lee, Kyun Jick

    2005-01-01

    Data mining (DM) models are an alternative to traditional statistical methods for examining whether higher customer satisfaction leads to higher revisit intention. This study used a total of 906 outpatients' satisfaction data collected from a nationwide survey interviews conducted by professional interviewers on a face-to-face basis in South Korea, 1998. Analyses showed that the relationship between overall satisfaction with hospital services and outpatients' revisit intention, along with word-of-mouth recommendation as intermediate variables, developed into a nonlinear relationship. The five strongest predictors of revisit intention were overall satisfaction, intention to recommend to others, awareness of hospital promotion, satisfaction with physician's kindness, and satisfaction with treatment level.

  9. The impact of generic substitution on price competition in Finland.

    Science.gov (United States)

    Aalto-Setälä, Ville

    2008-05-01

    Generic substitution by pharmacists was introduced in April 2003 in Finnish pharmaceutical markets. This article examines the impact of generic substitution on price development. This study examined all of the 2,100 substitutable drugs in Finland. The impact of generic substitution on price competition was significant. The average price of substitutable drugs decreased by more than 10%. However, the price development was uneven; some prices increased whereas others decreased by more than 50%. The most important factors that influenced the price development were the number of competitors, whether the drug was originator or generic and the width of the price band.

  10. Fluorescence lifetime components reveal kinetic intermediate states upon equilibrium denaturation of carbonic anhydrase II.

    Science.gov (United States)

    Nemtseva, Elena V; Lashchuk, Olesya O; Gerasimova, Marina A; Melnik, Tatiana N; Nagibina, Galina S; Melnik, Bogdan S

    2017-12-21

    In most cases, intermediate states of multistage folding proteins are not 'visible' under equilibrium conditions but are revealed in kinetic experiments. Time-resolved fluorescence spectroscopy was used in equilibrium denaturation studies. The technique allows for detecting changes in the conformation and environment of tryptophan residues in different structural elements of carbonic anhydrase II which in its turn has made it possible to study the intermediate states of carbonic anhydrase II under equilibrium conditions. The results of equilibrium and kinetic experiments using wild-type bovine carbonic anhydrase II and its mutant form with the substitution of leucine for alanine at position 139 (L139A) were compared. The obtained lifetime components of intrinsic tryptophan fluorescence allowed for revealing that, the same as in kinetic experiments, under equilibrium conditions the unfolding of carbonic anhydrase II ensues through formation of intermediate states.

  11. Emergency department revisits for patients with kidney stones in California.

    Science.gov (United States)

    Scales, Charles D; Lin, Li; Saigal, Christopher S; Bennett, Carol J; Ponce, Ninez A; Mangione, Carol M; Litwin, Mark S

    2015-04-01

    Kidney stones affect nearly one in 11 persons in the United States, and among those experiencing symptoms, emergency care is common. In this population, little is known about the incidence of and factors associated with repeat emergency department (ED) visits. The objective was to identify associations between potentially mutable factors and the risk of an ED revisit for patients with kidney stones in a large, all-payer cohort. This was a retrospective cohort study of all patients in California initially treated and released from EDs for kidney stones between February 2008 and November 2009. A multivariable regression model was created to identify associations between patient-level characteristics, area health care resources, processes of care, and the risk of repeat ED visits. The primary outcome was a second ED visit within 30 days of the initial discharge from emergent care. Among 128,564 patients discharged from emergent care, 13,684 (11%) had at least one additional emergent visit for treatment of their kidney stone. In these patients, nearly one in three required hospitalization or an urgent temporizing procedure at the second visit. On multivariable analysis, the risk of an ED revisit was associated with insurance status (e.g., Medicaid vs. private insurance; odds ratio [OR] = 1.52, 95% confidence interval [CI] = 1.43 to 1.61; p kidney stones. Access to urologic care and processes of care are associated with lower risk of repeat emergent encounters. Efforts are indicated to identify preventable causes of ED revisits for kidney stone patients and design interventions to reduce the risk of high-cost, high-acuity, repeat care. © 2015 by the Society for Academic Emergency Medicine.

  12. Solvent Induced Conformational Kinetics (SICK)

    NARCIS (Netherlands)

    Jonkman, Leffert; Kommandeur, Jan

    1970-01-01

    Specific conformations of molecules may be induced by the solvent when a large free volume is associated with the oonformational change. The conformational energy barrier is then a property of the solvent, rather than of the molecule. Such effects are reported for several substituted

  13. Small-angle scattering theory revisited: Photocurrent and spatial localization

    DEFF Research Database (Denmark)

    Basse, N.P.; Zoletnik, S.; Michelsen, Poul

    2005-01-01

    In this paper theory on collective scattering measurements of electron density fluctuations in fusion plasmas is revisited. We present the first full derivation of the expression for the photocurrent beginning at the basic scattering concepts. Thereafter we derive detailed expressions for the auto......- and crosspower spectra obtained from measurements. These are discussed and simple simulations made to elucidate the physical meaning of the findings. In this context, the known methods of obtaining spatial localization are discussed and appraised. Where actual numbers are applied, we utilize quantities from two...... laser based two-volume collective scattering instrument for spatially localized turbulence measurements,"Rev. Sci. Instrum. 72, 2579-2592 (2001)]....

  14. Revisiting the Level Scheme of the Proton Emitter 151Lu

    Science.gov (United States)

    Wang, F.; Sun, B. H.; Liu, Z.; Scholey, C.; Ashley, S. F.; Bianco, L.; Cullen, D. M.; Cullen, I. J.; Darby, I. G.; Eeckhaudt, S.; Garnsworthy, A. B.; Gelletly, W.; Gomez-Hornillos, M. B.; Grahn, T.; Greenlees, P. T.; Jenkins, D. G.; Jones, G. A.; Jones, P.; Joss, D. T.; Julin, R.; Juutinen, S.; Kettelhut, S.; Khan, S.; Kishada, A.; Leino, M.; Niikura, M.; Nyman, M.; Page, R. D.; Pakarinen, J.; Pietri, S.; Podolyak, Z.; Rahkila, P.; Rigby, S.; Saren, J.; Seweryniak, D.; Shizuma, T.; Simpson, J.; Sorri, J.; Steer, S.; Thompson, N. J.; Uusitalo, J.; Walker, P. M.; Williams, S.

    An experiment aiming to search for new isomers in the region of proton emitter 151Lu was performed at the Accelerator Laboratory of the University of Jyväskylä (JYFL), by combining the high resolution γ-ray array JUROGAM, gas-filled RITU separator and GREAT detectors with the triggerless total data readout acquisition (TDR) system. In this proceeding, we revisit the level scheme of 151Lu by using the proton-tagging technique. A level scheme consistent with the latest experimental results is obtained, and 3 additional levels are identified at high excitation energies.

  15. A control center design revisited: learning from users’ appropriation

    DEFF Research Database (Denmark)

    Souza da Conceição, Carolina; Cordeiro, Cláudia

    2014-01-01

    This paper aims to present the lessons learned during a control center design project by revisiting another control center from the same company designed two and a half years before by the same project team. In light of the experience with the first project and its analysis, the designers...... and researchers had important feedback already used to suggest changes for the second project. The opportunity to learn from a previous project was unique, but the knowledge gotten out of it shows the importance of having this feedback from project to project instead of just ‘repeating’ previously used design...

  16. Sampling the equilibrium: the j-walking algorithm revisited

    CERN Document Server

    Rimas, Zilvinas

    2016-01-01

    The j-walking Monte-Carlo algorithm is revisited and updated to study the equilibrium properties of a system exhibiting broken ergodicity. The updated algorithm is tested on the Ising model and applied to the lattice-gas model for sorption in aerogel at low temperatures, when dynamics of the system is critically slowed down. It is demonstrated that the updated j-walking simulations are able to produce equilibrium isotherm which are typically hidden by the hysteresis effect within the standard single-flip simulations.

  17. Genomics and blood substitutes for 21st century Europe ("EuroBloodSubstitutes").

    Science.gov (United States)

    Lowe, Kenneth C

    2006-01-01

    Blood transfusion is a medical intervention practised throughout the world. Blood is a biologically active material that can transmit diseases (e.g., HIV/AIDS and, perhaps, vCJD). People are becoming increasingly concerned about blood safety, despite improved screening and processing. Consequently, they are reluctant to donate blood or receive transfusions. Such problems can be solved by the development and incorporation into transfusion practices of so-called "blood substitutes" to replace some blood uses. The EuroBloodSubstitutes Project is funded by the European Union Framework 6 Programme to develop a technological platform for producing novel haem proteins and blood substitute components using micro-organisms (bacteria, fungi, yeast) as "cell factories." The Project will focus on bacteria (Escherichia coli), yeast (Pichia pastoris) and, longer-term, filamentous fungi (Aspergillus niger), all organisms used to synthesize commercially important products. The multi-centre Consortium consists of the Universities of (1) Nottingham (UK), (2) Essex (UK), (3) Denmark Technical (Denmark), (4) Lund (Sweden), (5) Milan (Italy), (6) Nancy (France), (7) Parma (Italy), (8) Rome "La Sapienza" (Italy), (9) Semmelweis (Hungary), together with (10) Alligator Bioscience, AB (Sweden), (11) LCC Engineering & Trading GmbH (Switzerland), (12) Scottish National Blood Transfusion Service (UK), and (13) Sanquin Bloodbank (The Netherlands). The EuroBloodSubstitutes Project will be informed by lay and professional stakeholders (e.g., clinicians, blood donors, patient groups, prescribers and policy makers). Outcomes of the Project are (1) the production of an information pack, decision aids and physician training aids, giving balanced overviews of the benefits and risks of transfusion of blood or potential substitutes, and (2) an interactive web site (http//:www.eurobloodsubstitutes.com) for information dissemination. This will improve knowledge and address misunderstandings about

  18. Origins of Enantioselectivity during Allylic Substitution Reactions Catalyzed by Metallacyclic Iridium Complexes

    Science.gov (United States)

    Madrahimov, Sherzod T.; Hartwig, John F.

    2012-01-01

    In depth mechanistic studies of iridium catalyzed regioselective and enantioselective allylic substitution reactions are presented. A series of cyclometallated allyliridium complexes that are kinetically and chemically competent to be intermediates in the allylic substitution reactions was prepared and characterized by 1D and 2D NMR spectroscopies and solid state structural analysis. The rates of epimerization of the less thermodynamically stable diastereomeric allyliridium complexes to the thermodynamically more stable allyliridium stereoisomers were measured. The rates of nucleophilic attack by aniline and by N-methylaniline on the isolated allyliridium complexes were also measured. Attack on the thermodynamically less stable allyliridium complex was found to be orders of magnitude faster than attack on the thermodynamically more stable complex, yet the major enantiomer of the catalytic reaction is formed from the more stable diastereomer. Comparison of the rates of nucleophilic attack to the rates of epimerization of the diastereomeric allyliridium complexes containing a weakly-coordinating counterion showed that nucleophilic attack on the less stable allyliridium species is much faster than conversion of the less stable isomer to the more stable isomer. These observations imply that Curtin-Hammett conditions are not met during iridium catalyzed allylic substitution reactions by η3-η1-η3 interconversion. Rather, these data imply that when these conditions exist for this reaction, they are created by reversible oxidative addition and the high selectivity of this oxidative addition step to form the more stable diastereomeric allyl complex leads to the high enantioselectivity. The stereochemical outcome of the individual steps of allylic substitution was assessed by reaction of deuterium-labeled substrates. The reaction was shown to occur by oxidative addition with inversion of configuration, followed by an outer sphere nucleophilic attack that leads to a second

  19. Kinetics of photo-activated charge carriers in Sn:CdS

    Energy Technology Data Exchange (ETDEWEB)

    Patidar, Manju Mishra, E-mail: manjumishra.iuc@gmail.com; Gorli, V. R.; Gangrade, Mohan; Nath, R.; Ganesan, V. [UGC-DAE CSR, University Campus, Khandwa Road, Indore (M.P.)-452001 (India); Panda, Richa [S.S. Jain Subodh Girls College, Airport Road Sanganer, Jaipur - 302029 (India)

    2016-05-23

    Kinetics of the photo-activated charge carriers has been investigated in Tin substituted Cadmium Sulphide, Cd{sub 1-x}Sn{sub x}S (x=0, 0.05, 0.10 and 0.15), thin films prepared by spray pyrolysis. X-Ray Diffraction shows an increase in strain that resulted in the decreased crystallite size upon Sn substitution. At the first sight, the photo current characteristics show a quenching effect on Sn substitution. However, survival of persistent photocurrents is seen even up to 15% of Sn substitution. Transient photo current decay could be explained with a 2τ relaxation model. CdS normally has an n-type character and the Sn doping expected to inject hole carriers. The two fold increase in τ{sub 1}, increase in activation energy and the decrease in photocurrents upon Sn substitution point towards a band gap cleaning scenario that include compensation and associated carrier injection dynamics. In addition Atomic Force Microscopy shows a drastic change in microstructure that modulates the carrier dynamics as a whole.

  20. Isotope fractionation of benzene during partitioning - Revisited.

    Science.gov (United States)

    Kopinke, F-D; Georgi, A; Imfeld, G; Richnow, H-H

    2017-02-01

    Isotope fractionation between benzene-D0 and benzene-D6 caused by multi-step partitioning of the benzenes between water and two organic solvents, n-octane and 1-octanol, as well as between water and the gas phase, was measured. The obtained fractionation factors αH = KH/KD are αH = 1.080 ± 0.015 and αH = 1.074 ± 0.015 for extraction into n-octane and 1-octanol, respectively, and αH = 1.049 ± 0.010 for evaporation from aqueous solution. The comparison of solvent- and gas-phase partitioning reveals that about 2/3 of the driving force of fractionation is due to different interactions in the aqueous phase, whereas 1/3 is due to different interactions in the organic phase. The heavy benzene isotopologue behaves more 'hydrophilically' and the light one more 'hydrophobically'. This synergistic alignment gives rise to relatively large fractionation effects in partitioning between water and non-polar organic matter. In contrast to a previous study, there is no indication of strong fractionation by specific interactions between benzene and octanol. Partitioning under non-equilibrium conditions yields smaller apparent fractionation effects due to opposite trends of thermodynamic and kinetic fractionation parameters, i.e. partition and diffusion coefficients of the isotopologues. This may have consequences which should be taken into account when considering isotope fractionation due to sorption in environmental compartments. Copyright © 2016 Elsevier Ltd. All rights reserved.