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Sample records for effect revisited thermodynamic

  1. Drop size effect on contact angle explained by nonextensive thermodynamics. Young's equation revisited.

    PubMed

    Letellier, Pierre; Mayaffre, Alain; Turmine, Mireille

    2007-10-15

    We applied the concepts of nonextensive thermodynamics [Turmine et al., J. Phys. Chem. B 108 (2004) 18980], to describe the equilibrium of a liquid drop placed on a solid substrate. This approach provides a consistent formal framework for analyzing the contact angle according to the nature and structure of the substrate, and also the size of the drops. The introduction, for the solid/liquid interface, of the concept of "fuzzy interface" characterized by a thermodynamic dimension, different from 2/3 (surface) allowed description of the case of substrates with ill-defined geometry (such as porous, structured systems, fractal structure systems, etc.) and straightforward explanation of the phenomenon of super hydrophobicity without using a layer of trapped air in possible anfractuosities. The application of the nonextensive thermodynamics relationships, allowed explanation of all the usual behaviors described in the literature (Young, modified Young, Wenzel, Cassie-Baxter) including the case of the composite interfaces made of materials with different natures and spatial structures (smooth, rough, homogeneous and heterogeneous surfaces). We show that the contact angle can vary with the drop volume according to a power law, and this was validated against values published in the literature. This study also has consequences for the relations between "thermodynamic dimension" and "fractal dimension."

  2. Revisit on the thermodynamic stability of the noncommutative Schwarzschild black hole

    NASA Astrophysics Data System (ADS)

    Ma, Meng-Sen; Liu, Yan-Song; Li, Huai-Fan

    In two frameworks, we discuss the thermodynamic stability of noncommutative geometry inspired Schwarzschild black hole (NCSBH). Under the horizon thermodynamics of black holes, we show that the NCSBH cannot be thermodynamically stable if requiring positive temperature. We note the inconsistency in the work of Larrañaga et al. and propose an effective first law of black hole thermodynamics for the NCSBH to eliminate the inconsistency. Based on the effective first law, we recalculate the heat capacity and the thermodynamic curvature by means of geometrothermodynamics (GTD) to revisit the thermodynamic stability.

  3. Automated Guidance for Thermodynamics Essays: Critiquing Versus Revisiting

    NASA Astrophysics Data System (ADS)

    Donnelly, Dermot F.; Vitale, Jonathan M.; Linn, Marcia C.

    2015-12-01

    Middle school students struggle to explain thermodynamics concepts. In this study, to help students succeed, we use a natural language processing program to analyze their essays explaining the aspects of thermodynamics and provide guidance based on the automated score. The 346 sixth-grade students were assigned to either the critique condition where they criticized an explanation or the revisit condition where they reviewed visualizations. Within each condition, the student was assigned one of two types of tailored guidance based on the sophistication of their original essay. Both forms of guidance led to significant improvement in student understanding on the posttest. Guidance was more effective for students with low prior knowledge than for those with high prior knowledge (consistent with regression toward the mean). However, analysis of student responses to the guidance illustrates the value of aligning guidance with prior knowledge. All students were required to revise their essay as an embedded assessment. While effective, teachers involved in this study reported that revising is resisted by students and does not align with typical, vocabulary-focused classroom writing activities.

  4. Thermodynamics of sulfur poisoning in solid oxide fuel cells revisited: The effect of H2S concentration, temperature, current density and fuel utilization

    NASA Astrophysics Data System (ADS)

    da Silva, Aline Lima; Heck, Nestor Cezar

    2015-11-01

    Thermodynamics of sulfur poisoning in SOFCs is revisited in the present study, aiming at contributing to the understanding of the effects of different operating parameters on deactivation by sulfur. Ni-S Gibbs energy diagram shows that, whenever sulfur chemical potential is increased, the catalyst poisoning becomes greater, due to increase in nickel sulfide activity, which is a strictly increasing function of sulfur coverage on Ni surface. For studying current density effect, simulations are carried out in the range of 0 (OCV) - 1 A cm-2, at 1123 K, considering methane as a fuel. At 10 ppm H2S, an increase in current density from 0 (OCV) to 0.5 A cm-2 results in a slight increase in the nickel sulfide activity from 3.0 × 10-6 to 1.2 × 10-5; however, at 1 A cm-2, nickel sulfide activity is 25.000 times higher than at 0.5 A cm-2. At 1 A cm-2, H2 and CO are almost entirely converted to H2O and CO2 by electrochemical reaction. Therefore, the effect of current density becomes remarkable when fuel utilization approaches 100%. These theoretical findings are corroborated by the recent experimental evidences related to the detrimental influence of current density on SOFC performance during sulfur poisoning.

  5. Revisiting the thermodynamic relations in AdS /CMT models

    NASA Astrophysics Data System (ADS)

    Hyun, Seungjoon; Park, Sang-A.; Yi, Sang-Heon

    2017-03-01

    Motivated by the recent unified approach to the Smarr-like relation of anti-de Sitter (AdS) planar black holes in conjunction with the quasilocal formalism on conserved charges, we revisit the quantum statistical and thermodynamic relations of hairy AdS planar black holes. By extending the previous results, we identify the hairy contribution in the bulk and show that the holographic computation can be improved so that it is consistent with the bulk computation. We argue that the first law can be retained in its universal form and that the relation between the on-shell renormalized Euclidean action and its free energy interpretation in gravity may also be undeformed even with the hairy contribution in hairy AdS black holes.

  6. Effective string theory revisited

    NASA Astrophysics Data System (ADS)

    Dubovsky, Sergei; Flauger, Raphael; Gorbenko, Victor

    2012-09-01

    We revisit the effective field theory of long relativistic strings such as confining flux tubes in QCD. We derive the Polchinski-Strominger interaction by a calculation in static gauge. This interaction implies that a non-critical string which initially oscillates in one direction gets excited in orthogonal directions as well. In static gauge no additional term in the effective action is needed to obtain this effect. It results from a one-loop calculation using the Nambu-Goto action. Non-linearly realized Lorentz symmetry is manifest at all stages in dimensional regularization. We also explain that independent of the number of dimensions non-covariant counterterms have to be added to the action in the commonly used zeta-function regularization.

  7. Automated Guidance for Thermodynamics Essays: Critiquing versus Revisiting

    ERIC Educational Resources Information Center

    Donnelly, Dermot F.; Vitale, Jonathan M.; Linn, Marcia C.

    2015-01-01

    Middle school students struggle to explain thermodynamics concepts. In this study, to help students succeed, we use a natural language processing program to analyze their essays explaining the aspects of thermodynamics and provide guidance based on the automated score. The 346 sixth-grade students were assigned to either the critique condition…

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

    PubMed

    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.

  9. Thermodynamics with friction. I. The Clausius inequality revisited

    NASA Astrophysics Data System (ADS)

    Bizarro, João P. S.

    2010-09-01

    The different forms of the Clausius inequality are generalized to explicitly include frictional work, which can be partly dissipated as heat in the surroundings and thus contribute to increase its entropy so, in a cyclic process, the net entropy leaving the surroundings with the heat directly exchanged with the system is no longer constrained by the second law to be nonpositive. Likewise, the lower bound for the system's entropy change in an arbitrary transformation is not now determined solely by the heat transferred from the surroundings but can be smaller by a term given by frictional dissipation in the latter. A wide range of applications is discussed, from thermal engines to mesoscopic devices, including the efficiency of dithermal engines and the problem of information erasure. Moreover, it is verified that the macroscopic approach utilized to extend standard macroscopic equilibrium theory in such a manner as to incorporate friction can be cast as well in the continuous, fieldlike formulation of nonequilibrium thermodynamics.

  10. The Thermodynamics of Marine Biogeochemical Cycles: Lotka Revisited

    NASA Astrophysics Data System (ADS)

    Vallino, Joseph J.; Algar, Christopher K.

    2016-01-01

    Nearly 100 years ago, Alfred Lotka published two short but insightful papers describing how ecosystems may organize. Principally, Lotka argued that ecosystems will grow in size and that their cycles will spin faster via predation and nutrient recycling so as to capture all available energy, and that evolution and natural selection are the mechanisms by which this occurs and progresses. Lotka's ideas have often been associated with the maximum power principle, but they are more consistent with recent developments in nonequilibrium thermodynamics, which assert that complex systems will organize toward maximum entropy production (MEP). In this review, we explore Lotka's hypothesis within the context of the MEP principle, as well as how this principle can be used to improve marine biogeochemistry models. We need to develop the equivalent of a climate model, as opposed to a weather model, to understand marine biogeochemistry on longer timescales, and adoption of the MEP principle can help create such models.

  11. Enthalpy-Entropy Compensation (EEC) Effect: A Revisit.

    PubMed

    Pan, Animesh; Biswas, Tapas; Rakshit, Animesh K; Moulik, Satya P

    2015-12-31

    A short account of the developments and perspectives of IKR (iso-kinetic relation) and EEC (enthalpy (H) - entropy (S) compensation) has been presented. The IKR and EEC are known to be extra thermodynamic or empirical correlations though linear H-S correlation can be thermodynamically deduced. Attempt has also been made to explain the phenomena in terms of statistical thermodynamics. In this study, we have briefly revisited the fundamentals of both IKR and EEC from kinetic and thermodynamic grounds. A detailed revisit of the EEC phenomenon on varied kinetic and equilibrium processes has been also presented. Possible correlations among the free energy (ΔG), enthalpy (ΔH), and entropy (ΔS) changes of different similar and nonsimilar chemical processes under varied conditions have been discussed with possible future projections.

  12. Thermodynamic effects on developed cavitation

    NASA Technical Reports Server (NTRS)

    Holl, J. W.; Billet, M. L.; Weir, D. S.

    1975-01-01

    The results of an investigation of thermodynamic effects are presented. Distributions of temperature and pressure in a developed cavity were measured for zero- and quarter-caliber ogives. A semiempirical entrainment theory was developed to correlate the measured temperature depression in the cavity. This theory correlates the maximum temperature depression expressed in dimensionless form as the Jakob number in terms of the dimensionless numbers of Nusselt, Reynolds, Froude, and Peclet, and dimensionless cavity length, L/D. The results show that in general, the temperature depression increases with L/D and temperature and the cavitation number based on measured cavity pressure is a function of L/D for a given model contour, independent of the thermodynamic effect.

  13. Finite size effect on classical ideal gas revisited

    NASA Astrophysics Data System (ADS)

    Ghosh, P.; Ghosh, S.; Mitra, J.; Bera, N.

    2015-09-01

    Finite size effects on classical ideal gas are revisited. The micro-canonical partition function for a collection of ideal particles confined in a box is evaluated using Euler-Maclaurin’s as well as Poisson's summation formula. In Poisson's summation formula there are some exponential terms which are absent in Euler-Maclaurin’s formula. In the thermodynamic limit the exponential correction is negligibly small but in the macro/nano dimensions and at low temperatures they may have a great significance. The consequences of finite size effects have been illustrated by redoing the calculations in one and three dimensions keeping the exponential corrections. Global and local thermodynamic properties, diffusion driven by the finite size effect, and effect on speed of sound have been discussed. Thermo-size effects, similar to thermoelectric effects, have been described in detail and may be a theoretical basis with which to design nano-scaled devices. This paper can also be very helpful for undergraduate and graduate students in physics and chemistry as an instructive exercise for a good course in statistical mechanics.

  14. Aharonov-Bohm effect revisited

    NASA Astrophysics Data System (ADS)

    Eskin, Gregory

    2015-04-01

    Aharonov-Bohm effect is a quantum mechanical phenomenon that attracted the attention of many physicists and mathematicians since the publication of the seminal paper of Aharonov and Bohm [1] in 1959. We consider different types of Aharonov-Bohm effects such as the magnetic AB effect, electric AB effect, combined electromagnetic AB effect, AB effect for the Schrödinger equations with Yang-Mills potentials, and the gravitational analog of AB effect. We shall describe different approaches to prove the AB effect based on the inverse scattering problems, the inverse boundary value problems in the presence of obstacles, spectral asymptotics, and the direct proofs of the AB effect.

  15. Fractional quantum Hall effect revisited

    NASA Astrophysics Data System (ADS)

    Jacak, J.; Łydżba, P.; Jacak, L.

    2015-10-01

    The topology-based explanation of the fractional quantum Hall effect (FQHE) is summarized. The cyclotron braid subgroups crucial for this approach are introduced in order to identify the origin of the Laughlin correlations in 2D (two-dimensional) Hall systems. Flux-tubes and vortices for composite fermions in their standard constructions are explained in terms of cyclotron braids. The derivation of the hierarchy of the FQHE is proposed by mapping onto the integer effect within the topology-based approach. The experimental observations of the FQHE supporting the cyclotron braid picture are reviewed with a special attention paid to recent experiments with a suspended graphene. The triggering role of a carrier mobility for organization of the fractional state in Hall configuration is emphasized. The prerequisites for the FQHE are indicated including topological conditions substantially increasing the previously accepted set of physical necessities. The explanation of numerical studies by exact diagonalizations of the fractional Chern insulator states is formulated in terms of the topology condition applied to the Berry field flux quantization. Some new ideas withz regard to the synthetic fractional states in the optical lattices are also formulated.

  16. Targeting Cancer Metabolism - Revisiting the Warburg Effects

    PubMed Central

    Tran, Quangdon; Lee, Hyunji; Park, Jisoo; Kim, Seon-Hwan; Park, Jongsun

    2016-01-01

    After more than half of century since the Warburg effect was described, this atypical metabolism has been standing true for almost every type of cancer, exhibiting higher glycolysis and lactate metabolism and defective mitochondrial ATP production. This phenomenon had attracted many scientists to the problem of elucidating the mechanism of, and reason for, this effect. Several models based on oncogenic studies have been proposed, such as the accumulation of mitochondrial gene mutations, the switch from oxidative phosphorylation respiration to glycolysis, the enhancement of lactate metabolism, and the alteration of glycolytic genes. Whether the Warburg phenomenon is the consequence of genetic dysregulation in cancer or the cause of cancer remains unknown. Moreover, the exact reasons and physiological values of this peculiar metabolism in cancer remain unclear. Although there are some pharmacological compounds, such as 2-deoxy-D-glucose, dichloroacetic acid, and 3-bromopyruvate, therapeutic strategies, including diet, have been developed based on targeting the Warburg effect. In this review, we will revisit the Warburg effect to determine how much scientists currently understand about this phenomenon and how we can treat the cancer based on targeting metabolism. PMID:27437085

  17. College-Level Sheltered Instruction: Revisiting the Issue of Effectiveness

    ERIC Educational Resources Information Center

    Knoblock, Natalia; Youngquist, Judy

    2016-01-01

    Finding an effective instruction mode for ESL students in the US educational system has not been an easy task. The country's secondary and tertiary institutions continue to struggle to meet the needs of their large non-native student populations. The article revisits the debate whether sheltered instruction is an effective model to follow. In our…

  18. Revisiting the Trust Effect in Urban Elementary Schools

    ERIC Educational Resources Information Center

    Adams, Curt M.; Forsyth, Patrick B.

    2013-01-01

    More than a decade after Goddard, Tschannen-Moran, and Hoy (2001) found that collective faculty trust in clients predicts student achievement in urban elementary schools, we sought to identify a plausible link for this relationship. Our purpose in revisiting the trust effect was twofold: (1) to test the main effect of collective faculty trust on…

  19. Revisiting thermodynamics and kinetic diffusivities of uranium–niobium with Bayesian uncertainty analysis

    DOE PAGES

    Duong, Thien C.; Hackenberg, Robert Errol; Landa, Alex; ...

    2016-09-20

    In this paper, thermodynamic and kinetic diffusivities of uranium–niobium (U–Nb) are re-assessed by means of the CALPHAD (CALculation of PHAse Diagram) methodology. In order to improve the consistency and reliability of the assessments, first-principles calculations are coupled with CALPHAD. In particular, heats of formation of γ -U–Nb are estimated and verified using various density-functional theory (DFT) approaches. These thermochemistry data are then used as constraints to guide the thermodynamic optimization process in such a way that the mutual-consistency between first-principles calculations and CALPHAD assessment is satisfactory. In addition, long-term aging experiments are conducted in order to generate new phase equilibriamore » data at the γ2/α+γ2 boundary. These data are meant to verify the thermodynamic model. Assessment results are generally in good agreement with experiments and previous calculations, without showing the artifacts that were observed in previous modeling. The mutual-consistent thermodynamic description is then used to evaluate atomic mobility and diffusivity of γ-U–Nb. Finally, Bayesian analysis is conducted to evaluate the uncertainty of the thermodynamic model and its impact on the system's phase stability.« less

  20. Revisiting thermodynamics and kinetic diffusivities of uranium–niobium with Bayesian uncertainty analysis

    SciTech Connect

    Duong, Thien C.; Hackenberg, Robert Errol; Landa, Alex; Honarmandi, Pejman; Talapatra, Anjana; Volz, Heather Michelle; Llobet, Anna Megias; Smith, Alice Iulia; King, Graham Missell; Bajaj, Saurabh; Ruban, Andrei; Vitos, Levente; Turchi, Patrice E. A.; Arroyave, Raymundo

    2016-09-20

    In this paper, thermodynamic and kinetic diffusivities of uranium–niobium (U–Nb) are re-assessed by means of the CALPHAD (CALculation of PHAse Diagram) methodology. In order to improve the consistency and reliability of the assessments, first-principles calculations are coupled with CALPHAD. In particular, heats of formation of γ -U–Nb are estimated and verified using various density-functional theory (DFT) approaches. These thermochemistry data are then used as constraints to guide the thermodynamic optimization process in such a way that the mutual-consistency between first-principles calculations and CALPHAD assessment is satisfactory. In addition, long-term aging experiments are conducted in order to generate new phase equilibria data at the γ2/α+γ2 boundary. These data are meant to verify the thermodynamic model. Assessment results are generally in good agreement with experiments and previous calculations, without showing the artifacts that were observed in previous modeling. The mutual-consistent thermodynamic description is then used to evaluate atomic mobility and diffusivity of γ-U–Nb. Finally, Bayesian analysis is conducted to evaluate the uncertainty of the thermodynamic model and its impact on the system's phase stability.

  1. The Importance of Being a Complement: CED Effects Revisited

    ERIC Educational Resources Information Center

    Jurka, Johannes

    2010-01-01

    This dissertation revisits subject island effects (Ross 1967, Chomsky 1973) cross-linguistically. Controlled acceptability judgment studies in German, English, Japanese and Serbian show that extraction out of specifiers is consistently degraded compared to extraction out of complements, indicating that the Condition on Extraction domains (CED,…

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

    PubMed Central

    Hejazi, Safiyah A.; Osman, Osman I.; Alyoubi, Abdulrahman O.; Aziz, Saadullah G.; Hilal, Rifaat H.

    2016-01-01

    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. PMID:27854244

  3. Anammox revisited: thermodynamic considerations in early studies of the microbial nitrogen cycle.

    PubMed

    Oren, Aharon

    2015-08-01

    This paper explores the early literature on the thermodynamics of processes in the microbial nitrogen cycle, evaluating parameters of transfer of energy which depends on the initial and final states of the system, the mechanism of the reactions involved and the rates of these reactions. Processes discussed include the anaerobic oxidation of ammonium (the anammox reaction), the use of inorganic nitrogen compounds as electron donors for anoxygenic photosynthesis, and the mechanism and bioenergetics of biological nitrogen fixation.

  4. Thermodynamics of Multicaloric Effects in Multiferroics

    NASA Astrophysics Data System (ADS)

    Planes, Antoni; Castan, Teresa; Saxena, Avadh

    2014-03-01

    Ferroic and multiferoic materials thermally respond to externally driven changes of ferroic properties. Usually these changes are induced by application or removal of the field thermodynamically conjugated to a specific property. The isothermal change of entropy and the adiabatic change of temperature are commonly used in order to quantify the caloric response of a given material. From this perspective we provide a general thermodynamic framework to study multicaloric effects in multiferroic materials. This is applied to the case of a magnetoelectric multiferroic, which is described by means of a Landau free energy with a biquadratic coupling between polarization and magnetization. We obtain a phase diagram, the isothermal entropy change and the adiabatic temperature change across different continuous and first order transitions as the applied electric and magnetic fields are varied. The obtained multicaloric effects are suitably decomposed into the corresponding electrocaloric and magnetocaloric contributions.

  5. Thermodynamic theory of the plasmoelectric effect

    PubMed Central

    van de Groep, Jorik; Sheldon, Matthew T.; Atwater, Harry A.; Polman, Albert

    2016-01-01

    Resonant metal nanostructures exhibit an optically induced electrostatic potential when illuminated with monochromatic light under off-resonant conditions. This plasmoelectric effect is thermodynamically driven by the increase in entropy that occurs when the plasmonic structure aligns its resonant absorption spectrum with incident illumination by varying charge density. As a result, the elevated steady-state temperature of the nanostructure induced by plasmonic absorption is further increased by a small amount. Here, we study in detail the thermodynamic theory underlying the plasmoelectric effect by analyzing a simplified model system consisting of a single silver nanoparticle. We find that surface potentials as large as 473 mV are induced under 100 W/m2 monochromatic illumination, as a result of a 11 mK increases in the steady-state temperature of the nanoparticle. Furthermore, we discuss the applicability of this analysis for realistic experimental geometries, and show that this effect is generic for optical structures in which the resonance is linked to the charge density. PMID:26987904

  6. Thermodynamic theory of the plasmoelectric effect

    SciTech Connect

    van de Groep, Jorik; Sheldon, Matthew T.; Atwater, Harry A.; Polman, Albert

    2016-03-18

    Resonant metal nanostructures exhibit an optically induced electrostatic potential when illuminated with monochromatic light under off-resonant conditions. This plasmoelectric effect is thermodynamically driven by the increase in entropy that occurs when the plasmonic structure aligns its resonant absorption spectrum with incident illumination by varying charge density. As a result, the elevated steady-state temperature of the nanostructure induced by plasmonic absorption is further increased by a small amount. Here, we study in detail the thermodynamic theory underlying the plasmoelectric effect by analyzing a simplified model system consisting of a single silver nanoparticle. We find that surface potentials as large as 473 mV are induced under 100 W/m2 monochromatic illumination, as a result of a 11 mK increases in the steady-state temperature of the nanoparticle. Hence, we discuss the applicability of this analysis for realistic experimental geometries, and show that this effect is generic for optical structures in which the resonance is linked to the charge density.

  7. Thermodynamic theory of the plasmoelectric effect

    DOE PAGES

    van de Groep, Jorik; Sheldon, Matthew T.; Atwater, Harry A.; ...

    2016-03-18

    Resonant metal nanostructures exhibit an optically induced electrostatic potential when illuminated with monochromatic light under off-resonant conditions. This plasmoelectric effect is thermodynamically driven by the increase in entropy that occurs when the plasmonic structure aligns its resonant absorption spectrum with incident illumination by varying charge density. As a result, the elevated steady-state temperature of the nanostructure induced by plasmonic absorption is further increased by a small amount. Here, we study in detail the thermodynamic theory underlying the plasmoelectric effect by analyzing a simplified model system consisting of a single silver nanoparticle. We find that surface potentials as large as 473more » mV are induced under 100 W/m2 monochromatic illumination, as a result of a 11 mK increases in the steady-state temperature of the nanoparticle. Hence, we discuss the applicability of this analysis for realistic experimental geometries, and show that this effect is generic for optical structures in which the resonance is linked to the charge density.« less

  8. Thermodynamics of silicon nitridation - Effect of hydrogen

    NASA Technical Reports Server (NTRS)

    Shaw, N. J.; Zeleznik, F. J.

    1982-01-01

    Equilibrium compositions for the nitridization of Si were calculated to detect the effectiveness of H2 in removal of the oxide film and in increasing the concentration of SiO and reducing the proportions of O2. Gibbs free energy for the formation of SiN2O was computed above 1685 K, and at lower temperatures. The thermodynamic properties of SiN2O2 were then considered from 1000-3000 K, taking into account the known thermodynamic data for 39 molecular combinations of the Si, Ni, and O. The gases formed were assumed ideal mixtures with pure phase condensed species. The mole fractions were obtained for a system of SiO2 with each Si particle covered with a thin layer of SiO2 before nitridation, and a system in which the nitriding atmosphere had access to the Si. The presence of H2 was determined to enhance the removal of NiO2 in the first system, decrease the partial pressure of O2, increase the partial pressures of SiO, Si, H2O, NH3, and SiH4, while its effects were negligible in the Si system.

  9. Dissipation effects in mechanics and thermodynamics

    NASA Astrophysics Data System (ADS)

    Güémez, J.; Fiolhais, M.

    2016-07-01

    With the discussion of three examples, we aim at clarifying the concept of energy transfer associated with dissipation in mechanics and in thermodynamics. The dissipation effects due to dissipative forces, such as the friction force between solids or the drag force in motions in fluids, lead to an internal energy increase of the system and/or to heat transfer to the surroundings. This heat flow is consistent with the second law, which states that the entropy of the universe should increase when those forces are present because of the irreversibility always associated with their actions. As far as mechanics is concerned, the effects of the dissipative forces are included in Newton’s equations as impulses and pseudo-works.

  10. Solubility of hematite revisited: effects of hydration.

    PubMed

    Jang, Je-Hun; Dempsey, Brian A; Burgos, William D

    2007-11-01

    Measured pH and dissolved ferric iron concentration ([Fe(III)diss]) in contact with well-characterized hematite indicated an equilibrium with hematite immediately after synthesis, but [Fe(III)diss] increased with hydration time to be consistent with the predicted solubility of goethite or hydrous ferric oxide (HFO), hydrated analogues of hematite. X-ray diffraction did not detect structural modification of hematite after 190 days of hydration, but Mössbauer spectroscopy detected hydration that penetrated several crystalline layers. When the hematite suspension was diluted with water, solids were invariably identified as hematite, but [Fe(III)diss] and pH indicated an equilibrium with goethite or HFO. This is the first experimental confirmation that the interfacial hydration of anhydrous hematite results in higher solubility than predicted by bulk thermodynamic properties of hematite. Correspondence of the results with previously published measurements and implications for environmental chemistry of ferric oxides are also discussed.

  11. Thermodynamical effects during carbon dioxide release

    NASA Astrophysics Data System (ADS)

    Singh, A. K.; Böttcher, N.; Görke, U.-J.; Kolditz, O.

    2012-04-01

    Pruess [1] investigated the risk of carbon dioxide leakage from shallow storage sites by modeling scenarios. Such a fluid release is associated with mechanical work performed by formation fluid against expansion without taking heat from ambient environment. Understanding of heat related to mechanical work is essential to predict the temperature at the leak. According to the first law of thermodynamics, internal energy of working fluid decreases with an amount which is equivalent to this work hence, working fluid lost its own heat. Such kind of heat loss depends strongly on whether the expansion process is adiabatic or isothermal. Isothermal expansion allows the working fluid to interact thermally with the solid matrix. Adiabatic expansion is an isenthalpic process that takes heat from the working fluid and the ambient environment remains unchanged. This work is part of the CLEAN research project [6]. In this study, thermodynamic effects of mechanical work during eventual carbon dioxide leakage are investigated numerically. In particular, we are interested to detect the temperature at leakage scenarios and its deviation with different thermodynamic processes. Finite element simulation is conducted with a two-dimensional rectangular geometry representing a shallow storage site which bottom was located at -300m below the land surface. A fully saturated porous medium is assumed where the pore space is filled completely with carbon dioxide. Carbon dioxide accumulated in the secondary trap at 30 Bar and 24 °C is allowed to leak from top right point of rectangle with atmospheric pressure. With (i) adiabatic and (ii) isothermal compressibility factors, temperature around leakage area has been calculated which show a significant difference. With some simplification, this study detects leak temperature which is very close with [1]. Temporal evaluation at the leaky area shows that the working fluid temperature can be reduced to -20 °C when the leakage scenario is performed

  12. A short revisit to Kuo-Brown effective interactions

    NASA Astrophysics Data System (ADS)

    Wang, XiaoBao; Dong, GuoXiang

    2015-10-01

    This paper is a short revisit to Kuo-Brown effective interaction derived from the Hamada-Johnston nucleon-nucleon potential, done by Gerry Brown and Tom Kuo. This effective interaction, derived in year 1966, is the first attempt to describe nuclear structure properties from the free nucleon-nucleon potential. Nowadays much progress has been achieved for the effective interactions in shell model. We would compare the effective interactions obtained in the 1966 paper with up-to-date shell-model interactions in sd-shell and pf-shell model space. Recent knowledge of effective interactions on nuclear structure, can also be traced in the Kuo- Brown effective interaction, i.e., the universal roles of central and tensor forces, which reminds us that such discovery should be noticed much earlier.

  13. Revisiting the Scattering Greenhouse Effect of CO2 Ice Clouds

    NASA Astrophysics Data System (ADS)

    Kitzmann, D.

    2016-02-01

    Carbon dioxide ice clouds are thought to play an important role for cold terrestrial planets with thick CO2 dominated atmospheres. Various previous studies showed that a scattering greenhouse effect by carbon dioxide ice clouds could result in a massive warming of the planetary surface. However, all of these studies only employed simplified two-stream radiative transfer schemes to describe the anisotropic scattering. Using accurate radiative transfer models with a general discrete ordinate method, this study revisits this important effect and shows that the positive climatic impact of carbon dioxide clouds was strongly overestimated in the past. The revised scattering greenhouse effect can have important implications for the early Mars, but also for planets like the early Earth or the position of the outer boundary of the habitable zone.

  14. The effect of time ordering revisited

    SciTech Connect

    Rosato, J.; Boland, D.; Capes, H.; Marandet, Y.; Stamm, R.

    2008-10-22

    The effects of time ordering on line shapes are investigated for the dynamic ionic broadening of the Lyman alpha line in hydrogen plasmas. The difference between calculations with and without time ordering is calculated for an electric field created by a single particle, and for a thermal average over plasma configurations with moderate temperature and density.

  15. Student's perceptions of effective clinical teaching revisited.

    PubMed

    Kelly, Claudette

    2007-11-01

    Despite a wealth of research on clinical teaching, the criteria for determining what constitutes effective clinical teaching remain poorly defined [Cholowski, K., 2002. Nursing students' and clinical educators' perceptions of characteristics of effective clinical educators in an Australian university school of nursing. Journal of Advanced Nursing 39 (5), 412-420]. This paper reports on two studies exploring second and third year nursing student's perceptions of effective clinical teaching over 14 years (1989-2003). The aim of the inquiry was to compare student's perceptions in diploma and baccalaureate programs within existing clinical contexts. This research used a generative approach to elicit learner's views of what teacher characteristics and contextual influences impact them in clinical settings. A convenience sample of 30 students at the end of second and third years volunteered to be interviewed in-depth for each study. The first study was conducted in a diploma program, whereas in the second study all but a few students were elected to complete a four year baccalaureate nursing degree. Findings from both studies are remarkably consistent. Students in both studies rated teacher knowledge as most important followed by feedback and communication skills. Teacher knowledge appeared critical in four areas: as it pertains to the clinical setting, the curriculum, the learner and teaching/learning theory. How well students perceived that they were accepted by staff, student-teacher ratios and peer support also appeared to impact student's views of effective clinical teaching. This research has implications for employment and evaluation practices for teachers in applied fields such as nursing. The study raises questions about the recent trend toward temporary employment of clinical teachers and in the separation of academic and clinical roles of nurse educators.

  16. Thermodynamic Losses in Multi-effect Distillation Process

    NASA Astrophysics Data System (ADS)

    Shen, S.

    2015-09-01

    The multi-effect distillation (MED) is one of desalination technologies. It is also applied in chemical engineering and other industries for evaporation, distillation, crystallization, etc. In a large multi-effect distillation plant, some tiny thermodynamic losses might have a great influence to the performance and design parameters. For the detailed analysis and design of a MED desalination plant, a series of experiments were carried out. The thermodynamic losses in a MED desalination plant is analyzed as an example to show its effect on the performance and structure parameters. The thermodynamics losses have a cumulative effect. With the increase of effect number and the concentration ratio, the thermodynamic losses shall be a dominant factor for the operation performance of a MED plant.

  17. Landauer's blowtorch effect as a thermodynamic cross process: Brownian cooling.

    PubMed

    Das, Moupriya; Das, Debojyoti; Barik, Debashis; Ray, Deb Shankar

    2015-11-01

    The local heating of a selected region in a double-well potential alters the relative stability of the two wells and gives rise to an enhancement of population transfer to the cold well. We show that this Landauer's blowtorch effect may be considered in the spirit of a thermodynamic cross process linearly connecting the flux of particles and the thermodynamic force associated with the temperature difference and consequently ensuring the existence of a reverse cross effect. This reverse effect is realized by directing the thermalized particles in a double-well potential by application of an external bias from one well to the other, which suffers cooling.

  18. Landauer's blowtorch effect as a thermodynamic cross process: Brownian cooling

    NASA Astrophysics Data System (ADS)

    Das, Moupriya; Das, Debojyoti; Barik, Debashis; Ray, Deb Shankar

    2015-11-01

    The local heating of a selected region in a double-well potential alters the relative stability of the two wells and gives rise to an enhancement of population transfer to the cold well. We show that this Landauer's blowtorch effect may be considered in the spirit of a thermodynamic cross process linearly connecting the flux of particles and the thermodynamic force associated with the temperature difference and consequently ensuring the existence of a reverse cross effect. This reverse effect is realized by directing the thermalized particles in a double-well potential by application of an external bias from one well to the other, which suffers cooling.

  19. Effect of sorption/curved interface thermodynamics on pressure transient

    SciTech Connect

    Lim, K.T.; Aziz, K.

    1995-01-26

    A simulation model capable of handling the effects of sorption was constructed. It accounts for the curved interface thermodynamics associated with adsorption and desorption. Data from several laboratory experiments were used to verify the model. The results indicated that simulation runs using sorption isotherms adequately model the pressure transient behavior observed in the laboratory experiments. Dry steam models severely underestimated the effective compressibility. Models using flat-interface (steam table) thermodynamics over-estimated the compressibility of the system, indicated by slower than actual rate of pressure transient propagation.

  20. Dynamical Casimir effect and minimal temperature in quantum thermodynamics

    NASA Astrophysics Data System (ADS)

    Benenti, Giuliano; Strini, Giuliano

    2015-02-01

    We study the fundamental limitations of cooling to absolute zero for a qubit, interacting with a single mode of the electromagnetic field. Our results show that the dynamical Casimir effect, which is unavoidable in any finite-time thermodynamic cycle, forbids the attainability of the absolute zero of temperature, even in the limit of an infinite number of cycles.

  1. Effective-Medium Models for Marine Gas Hydrates, Mallik Revisited

    NASA Astrophysics Data System (ADS)

    Terry, D. A.; Knapp, C. C.; Knapp, J. H.

    2011-12-01

    Hertz-Mindlin type effective-medium dry-rock elastic models have been commonly used for more than three decades in rock physics analysis, and recently have been applied to assessment of marine gas hydrate resources. Comparisons of several effective-medium models with derivative well-log data from the Mackenzie River Valley, Northwest Territories, Canada (i.e. Mallik 2L-38 and 5L-38) were made several years ago as part of a marine gas hydrate joint industry project in the Gulf of Mexico. The matrix/grain supporting model (one of the five models compared) was clearly a better representation of the Mallik data than the other four models (2 cemented sand models; a pore-filling model; and an inclusion model). Even though the matrix/grain supporting model was clearly better, reservations were noted that the compressional velocity of the model was higher than the compressional velocity measured via the sonic logs, and that the shear velocities showed an even greater discrepancy. Over more than thirty years, variations of Hertz-Mindlin type effective medium models have evolved for unconsolidated sediments and here, we briefly review their development. In the past few years, the perfectly smooth grain version of the Hertz-Mindlin type effective-medium model has been favored over the infinitely rough grain version compared in the Gulf of Mexico study. We revisit the data from the Mallik wells to review assertions that effective-medium models with perfectly smooth grains are a better predictor than models with infinitely rough grains. We briefly review three Hertz-Mindlin type effective-medium models, and standardize nomenclature and notation. To calibrate the extended effective-medium model in gas hydrates, we use a well accepted framework for unconsolidated sediments through Hashin-Shtrikman bounds. We implement the previously discussed effective-medium models for saturated sediments with gas hydrates and compute theoretical curves of seismic velocities versus gas hydrate

  2. Revisiting the thermodynamic theory of optimal ATP stoichiometries by analysis of various ATP-producing metabolic pathways.

    PubMed

    Werner, Sarah; Diekert, Gabriele; Schuster, Stefan

    2010-12-01

    The stoichiometry of ATP-producing metabolic pathways had been analysed theoretically by several authors by using evolutionary arguments and optimality principles. Waddell et al. (Biochem Educ 27:12-13, 1999) analysed (lactate-producing) glycolysis and used linear irreversible thermodynamics. The result was that half of the free-energy difference should be converted into free-energy of ATP and the remaining half should be used to drive the pathway. The calculated stoichiometry is in agreement with the observed yield of two moles of ATP per mole of glucose. Using the same approach, we here analyse eight other metabolic pathways. Although the deviation is not very large, the calculated values do not fit as nicely as for glycolysis as leading to lactate. For example, for O₂ respiration, the theoretical ATP yield equals 27.9. The real value varies among organisms between 26 and 38. For mixed-acid fermentation in Escherichia coli, the theoretical and experimental values are 2.24 and 2, respectively. For arginine degradation in M. pneumoniae, the calculated value is 2.43 mol of ATP, while in vivo only one mole is produced. During evolution, some pathways may not have reached their optimal ATP net production because energy yield is not their only function. Moreover, it should be acknowledged that the approach by linear irreversible thermodynamics is a rough approximation.

  3. Stochastic dynamics and non-equilibrium thermodynamics of a bistable chemical system: the Schlögl model revisited.

    PubMed

    Vellela, Melissa; Qian, Hong

    2009-10-06

    Schlögl's model is the canonical example of a chemical reaction system that exhibits bistability. Because the biological examples of bistability and switching behaviour are increasingly numerous, this paper presents an integrated deterministic, stochastic and thermodynamic analysis of the model. After a brief review of the deterministic and stochastic modelling frameworks, the concepts of chemical and mathematical detailed balances are discussed and non-equilibrium conditions are shown to be necessary for bistability. Thermodynamic quantities such as the flux, chemical potential and entropy production rate are defined and compared across the two models. In the bistable region, the stochastic model exhibits an exchange of the global stability between the two stable states under changes in the pump parameters and volume size. The stochastic entropy production rate shows a sharp transition that mirrors this exchange. A new hybrid model that includes continuous diffusion and discrete jumps is suggested to deal with the multiscale dynamics of the bistable system. Accurate approximations of the exponentially small eigenvalue associated with the time scale of this switching and the full time-dependent solution are calculated using Matlab. A breakdown of previously known asymptotic approximations on small volume scales is observed through comparison with these and Monte Carlo results. Finally, in the appendix section is an illustration of how the diffusion approximation of the chemical master equation can fail to represent correctly the mesoscopically interesting steady-state behaviour of the system.

  4. A large solvent isotope effect on protein association thermodynamics.

    PubMed

    Eginton, Christopher; Beckett, Dorothy

    2013-09-24

    Solvent reorganization can contribute significantly to the energetics of protein-protein interactions. However, our knowledge of the magnitude of the energetic contribution is limited, in part, by a dearth of quantitative experimental measurements. The biotin repressor forms a homodimer as a prerequisite to DNA binding to repress transcription initiation. At 20 °C, the dimerization reaction, which is thermodynamically coupled to binding of a small ligand, bio-5'-AMP, is characterized by a Gibbs free energy of -7 kcal/mol. This modest net dimerization free energy reflects underlying, very large opposing enthalpic and entropic driving forces of 41 ± 3 and -48 ± 3 kcal/mol, respectively. The thermodynamics have been interpreted as indicating coupling of solvent release to dimerization. In this work, this interpretation has been investigated by measuring the effect of replacing H2O with D2O on the dimerization thermodynamics. Sedimentation equilibrium measurements performed at 20 °C reveal a solvent isotope effect of -1.5 kcal/mol on the Gibbs free energy of dimerization. Analysis of the temperature dependence of the reaction in D2O indicates enthalpic and entropic contributions of 28 and -37 kcal/mol, respectively, considerably smaller than the values measured in H2O. These large solvent isotope perturbations to the thermodynamics are consistent with a significant contribution of solvent release to the dimerization reaction.

  5. The thermodynamic effect of atmospheric mass on early Earth's temperature

    NASA Astrophysics Data System (ADS)

    Chemke, R.; Kaspi, Y.; Halevy, I.

    2016-11-01

    Observations suggest that Earth's early atmospheric mass differed from the present day. The effects of a different atmospheric mass on radiative forcing have been investigated in climate models of variable sophistication, but a mechanistic understanding of the thermodynamic component of the effect of atmospheric mass on early climate is missing. Using a 3-D idealized global circulation model (GCM), we systematically examine the thermodynamic effect of atmospheric mass on near-surface temperature. We find that higher atmospheric mass tends to increase the near-surface temperature mostly due to an increase in the heat capacity of the atmosphere, which decreases the net radiative cooling effect in the lower layers of the atmosphere. Additionally, the vertical advection of heat by eddies decreases with increasing atmospheric mass, resulting in further near-surface warming. As both net radiative cooling and vertical eddy heat fluxes are extratropical phenomena, higher atmospheric mass tends to flatten the meridional temperature gradient.

  6. Quantum gravity effects on charged microblack holes thermodynamics

    NASA Astrophysics Data System (ADS)

    Abbasvandi, Niloofar; Soleimani, M. J.; Radiman, Shahidan; Wan Abdullah, W. A. T.

    2016-08-01

    The charged black hole thermodynamics is corrected in terms of the quantum gravity effects. Most of the quantum gravity theories support the idea that near the Planck scale, the standard Heisenberg uncertainty principle should be reformulated by the so-called Generalized Uncertainty Principle (GUP) which provides a perturbation framework to perform required modifications of the black hole quantities. In this paper, we consider the effects of the minimal length and maximal momentum as GUP type I and the minimal length, minimal momentum and maximal momentum as GUP type II on thermo dynamics of the charged TeV-scale black holes. We also generalized our study to the universe with the extra dimensions based on the ADD model. In this framework, the effect of the electrical charge on thermodynamics of the black hole and existence of the charged black hole remnants as a potential candidate for the dark matter particles are discussed.

  7. Effects of smooth random surface on fluid monolayer thermodynamics

    NASA Astrophysics Data System (ADS)

    Khlyupin, A. N.

    2016-11-01

    We consider the lattice gas approach to statistical mechanics of fluid adsorbed on random surfaces with fluid-fluid and fluid-surface potentials. It was shown that effective Hamiltonian contains quenched random interactions and random site fields. Their statistical features combine the properties of random geometry and fluid-fluid pair interaction potential. The high-temperature expansion leads to infinite-ranged random field model and Sherrington-Kirkpatrick spin-glass model. Thermodynamic properties are evaluated using replica theory procedure widely used to analyze quenched disorder systems. On the other hand we consider the random field model in random graph with finite connectivity instead of previous “infinite-ranged” approximations. This model has been investigated using finite connectivity technique. The replica symmetry ansatz for the order function is expressed in terms of an effective-field distribution. Analysis of random geometry effects on thermodynamic properties in such approach was done for the first time.

  8. Correlations of thermodynamic effects for developed cavitation

    NASA Technical Reports Server (NTRS)

    Billet, M. L.; Holl, J. W.; Weir, D. S.

    1978-01-01

    The net positive suction head (NPSH) requirements for a pump are determined by the combined effects of cavitation, fluid properties, pump geometry, and pump operating point. An important part of this determination is the temperature depression (Delta T). Correlations are presented of the temperature depression for various degrees of developed cavitation on venturis and ogives. These correlations, based on a semi-empirical entrainment theory, express Delta T in terms of the dimensionless numbers of Nusselt, Reynolds, Froude, Weber, and Peclet, and dimensionless cavity length (L/D). The Delta T data were obtained in Freon 114, hydrogen and nitrogen for the venturis and in Freon 113 and water for the ogives.

  9. Non-equilibrium Thermodynamics of the Longitudinal Spin Seebeck Effect

    NASA Astrophysics Data System (ADS)

    Basso, Vittorio; Ferraro, Elena; Sola, Alessandro; Magni, Alessandro; Kuepferling, Michaela; Pasquale, Massimo

    In this paper we employ non equilibrium thermodynamics of fluxes and forces to describe magnetization and heat transport. By the theory we are able to identify the thermodynamic driving force of the magnetization current as the gradient of the effective field ▿H*. This definition permits to define the spin Seebeck coefficient ɛM which relates ▿H* and the temperature gradient ▿T. By applying the theory to the geometry of the longitudinal spin Seebeck effect we are able to obtain the optimal conditions for generating large magnetization currents. Furthermore, by using the results of recent experiments, we obtain an order of magnitude for the value of ɛM ∼ 10-2 TK-1 for yttrium iron garnet (Y3Fe5O12).

  10. Understanding the edge effect in wetting: a thermodynamic approach.

    PubMed

    Fang, Guoping; Amirfazli, A

    2012-06-26

    Edge effect is known to hinder spreading of a sessile drop. However, the underlying thermodynamic mechanisms responsible for the edge effect still is not well-understood. In this study, a free energy model has been developed to investigate the energetic state of drops on a single pillar (from upright frustum to inverted frustum geometries). An analysis of drop free energy levels before and after crossing the edge allows us to understand the thermodynamic origin of the edge effect. In particular, four wetting cases for a drop on a single pillar with different edge angles have been determined by understanding the characteristics of FE plots. A wetting map describing the four wetting cases is given in terms of edge angle and intrinsic contact angle. The results show that the free energy barrier observed near the edge plays an important role in determining the drop states, i.e., (1) stable or metastable drop states at the pillar's edge, and (2) drop collapse by liquid spilling over the edge completely or staying at an intermediate sidewall position of the pillar. This thermodynamic model presents an energetic framework to describe the functioning of the so-called "re-entrant" structures. Results show good consistency with the literature and expand the current understanding of Gibbs' inequality condition.

  11. Structural models of activated γ-alumina surfaces revisited: Thermodynamics, NMR and IR spectroscopies from ab initio calculations

    NASA Astrophysics Data System (ADS)

    Ferreira, Ary R.; Küçükbenli, Emine; de Gironcoli, Stefano; Souza, Wladmir F.; Chiaro, Sandra Shirley X.; Konstantinova, Elena; Leitão, Alexandre A.

    2013-09-01

    The activation of highly catalytic γ-alumina surfaces by thermal treatment and the description of the related chemical processes at atomic scale is a topical issue. According to a recent study [J. Am. Chem. Soc. 134 (2012) 14430], the enhanced reactivity of γ-alumina has been associated to tri-coordinated aluminum sites which supposedly are exposed exclusively on the (1 1 0) surfaces of this oxide. In this work, we explore this possibility by modeling the (1 0 0) and (1 1 0) terminations using Krokidis et al. [J. Phys. Chem. B 105 (2001) 5121] bulk structure and performing an extensive search of the most stable hydrated surface models at conditions consistent with experiment. Among the 156 structures analyzed, we identify several “metastable” models for the (1 1 0) surface with a considerable probability of containing the AlIII centers at OH coverages of 9.0 and 6.0 OH/nm2. We then test the reactivity of these sites through their Lewis acidity by simulating the CO adsorbtion on the surface and our results confirm the high reactivity of AlIII centers. Based on the Gibbs free energy of the explored structures, we carry on a thermodynamical analysis at varying hydroxylation degrees and pretreatment temperatures and simulate the experimental volcano-type behavior reported in [J. Am. Chem. Soc. 134 (2012) 14430] and predict the optimum pretreatment temperature as 700 °C, in very good agreement with experimental findings. We further use infrared and solid state MAS NMR spectroscopies and reproduce the 1H MAS NMR spectra under high vacuum conditions (10-5 Torr). The strong resemblance of spectra to the experimental ones in the literature [J. Phys. Chem. C 116 (2012) 834] validate further the structural models we have generated in this study.

  12. Thermodynamic Casimir effect in films: the exchange cluster algorithm.

    PubMed

    Hasenbusch, Martin

    2015-02-01

    We study the thermodynamic Casimir force for films with various types of boundary conditions and the bulk universality class of the three-dimensional Ising model. To this end, we perform Monte Carlo simulations of the improved Blume-Capel model on the simple cubic lattice. In particular, we employ the exchange or geometric cluster cluster algorithm [Heringa and Blöte, Phys. Rev. E 57, 4976 (1998)]. In a previous work, we demonstrated that this algorithm allows us to compute the thermodynamic Casimir force for the plate-sphere geometry efficiently. It turns out that also for the film geometry a substantial reduction of the statistical error can achieved. Concerning physics, we focus on (O,O) boundary conditions, where O denotes the ordinary surface transition. These are implemented by free boundary conditions on both sides of the film. Films with such boundary conditions undergo a phase transition in the universality class of the two-dimensional Ising model. We determine the inverse transition temperature for a large range of thicknesses L(0) of the film and study the scaling of this temperature with L(0). In the neighborhood of the transition, the thermodynamic Casimir force is affected by finite size effects, where finite size refers to a finite transversal extension L of the film. We demonstrate that these finite size effects can be computed by using the universal finite size scaling function of the free energy of the two-dimensional Ising model.

  13. Surface Emissivity Effects on Thermodynamic Retrieval of IR Spectral Radiance

    NASA Technical Reports Server (NTRS)

    Zhou, Daniel K.; Larar, Allen M.; Smith, William L.; Liu, Xu

    2006-01-01

    The surface emissivity effect on the thermodynamic parameters (e.g., the surface skin temperature, atmospheric temperature, and moisture) retrieved from satellite infrared (IR) spectral radiance is studied. Simulation analysis demonstrates that surface emissivity plays an important role in retrieval of surface skin temperature and terrestrial boundary layer (TBL) moisture. NAST-I ultraspectral data collected during the CLAMS field campaign are used to retrieve thermodynamic properties of the atmosphere and surface. The retrievals are then validated by coincident in-situ measurements, such as sea surface temperature, radiosonde temperature and moisture profiles. Retrieved surface emissivity is also validated by that computed from the observed radiance and calculated emissions based on the retrievals of surface temperature and atmospheric profiles. In addition, retrieved surface skin temperature and emissivity are validated together by radiance comparison between the observation and retrieval-based calculation in the window region where atmospheric contribution is minimized. Both simulation and validation results have lead to the conclusion that variable surface emissivity in the inversion process is needed to obtain accurate retrievals from satellite IR spectral radiance measurements. Retrieval examples are presented to reveal that surface emissivity plays a significant role in retrieving accurate surface skin temperature and TBL thermodynamic parameters.

  14. Experimental studies on thermodynamic effects of developed cavitation

    NASA Technical Reports Server (NTRS)

    Ruggeri, R. S.

    1974-01-01

    A method for predicting thermodynamic effects of cavitation (changes in cavity pressure relative to stream vapor pressure) is presented. The prediction method accounts for changes in liquid, liquid temperature, flow velocity, and body scale. Both theoretical and experimental studies used in formulating the method are discussed. The prediction method provided good agreement between predicted and experimental results for geometrically scaled venturis handling four different liquids of widely diverse physical properties. Use of the method requires geometric similarity of the body and cavitated region and a known reference cavity-pressure depression at one operating condition.

  15. A theoretical investigation of thermodynamic effects on developed cavitation

    NASA Technical Reports Server (NTRS)

    Weir, D. S.

    1976-01-01

    The results of a theoretical investigation of thermodynamic effects on developed cavitation are presented. An approximate solution to the conservation equations for a two-phase laminar boundary layer is obtained. This analysis produces an expression for the temperature difference between the liquid and vapor phases which can be applied to developed cavity flows. Experimental data of cavity temperature depressions are correlated using this result. In addition, a theoretical estimate of the Nusselt number for the cavity is made using a turbulent boundary layer cavity model proposed by Brennen. The result agrees in part with empirically determined expressions for the cavity Nusselt number.

  16. Comments to Irreversibility in Thermodynamics

    NASA Technical Reports Server (NTRS)

    Zak, M.

    1995-01-01

    The problem of irreversibility in thermodynamics was revisited and analyzed on the microscopic, stochastic, and macroscopic levels of description. It was demonstrated that Newtonian dynamics can be represented in the Reynolds form, a new phenomenological force with non-Lipschitz properties was introduced, and additional non- Lipschitz thermodynamical forces were incorporated into macroscopic models of transport phenomena.

  17. The effects of quantum gravity on some thermodynamical quantities

    NASA Astrophysics Data System (ADS)

    Kamali, A. D.; Shababi, H.; Nozari, K.

    2016-10-01

    In this paper, using a deformed algebra [X,P] = iℏ/(1 - α2P2) which is originated from various theories of gravity, we study thermodynamical properties of the classical and extreme relativistic gases in canonical ensembles. In this regards, we exactly calculate the modified partition function, Helmholtz free energy, internal energy, entropy, heat capacity and the thermal pressure which conclude to the familiar form of the equation of state for the ideal gas. The advantage of applying this algebra is not only considering all natural cutoffs but also its structure is similar to the other effective quantum gravity models such as polymer, Snyder and noncommutative space-time frameworks. Moreover, after obtaining some thermodynamical quantities including internal energy and entropy, we conclude at high temperature limits due to the decreasing of the number of microstates, these quantities reach to maximal bounds which do not exist in standard cases and it concludes that at the presence of gravity for both micro-canonic and canonic ensembles, the internal energy and the entropy tend to these upper bounds.

  18. Nonequilibrium thermodynamics of the spin Seebeck and spin Peltier effects

    NASA Astrophysics Data System (ADS)

    Basso, Vittorio; Ferraro, Elena; Magni, Alessandro; Sola, Alessandro; Kuepferling, Michaela; Pasquale, Massimo

    2016-05-01

    We study the problem of magnetization and heat currents and their associated thermodynamic forces in a magnetic system by focusing on the magnetization transport in ferromagnetic insulators like YIG. The resulting theory is applied to the longitudinal spin Seebeck and spin Peltier effects. By focusing on the specific geometry with one Y3Fe5O12 (YIG) layer and one Pt layer, we obtain the optimal conditions for generating large magnetization currents into Pt or large temperature effects in YIG. The theoretical predictions are compared with experiments from the literature permitting to derive the values of the thermomagnetic coefficients of YIG: the magnetization diffusion length lM˜0.4 μ m and the absolute thermomagnetic power coefficient ɛM˜10-2TK-1 .

  19. Revisit the spin-FET: Multiple reflection, inelastic scattering, and lateral size effects

    PubMed Central

    Xu, Luting; Li, Xin-Qi; Sun, Qing-feng

    2014-01-01

    We revisit the spin-injected field effect transistor (spin-FET) in a framework of the lattice model by applying the recursive lattice Green's function approach. In the one-dimensional case the results of simulations in coherent regime reveal noticeable differences from the celebrated Datta-Das model, which lead us to an improved treatment with generalized result. The simulations also allow us to address inelastic scattering and lateral confinement effects in the control of spins. These issues are very important in the spin-FET device. PMID:25516433

  20. The effects of the size of nanocrystalline materials on their thermodynamic and mechanical properties.

    PubMed

    Yu, Xiaohua; Zhan, Zhaolin

    2014-01-01

    This work has considered the intrinsic influence of bond energy on the macroscopic, thermodynamic, and mechanical properties of crystalline materials. A general criterion is proposed to evaluate the properties of nanocrystalline materials. The interrelation between the thermodynamic and mechanical properties of nanomaterials is presented and the relationship between the variation of these properties and the size of the nanomaterials is explained. The results of our work agree well with thermodynamics, molecular dynamics simulations, and experimental results. This method is of significance in investigating the size effects of nanomaterials and provides a new approach for studying their thermodynamic and mechanical properties.

  1. Revisiting the classics: considering nonconsumptive effects in textbook examples of predator-prey interactions.

    PubMed

    Peckarsky, Barbara L; Abrams, Peter A; Bolnick, Daniel I; Dill, Lawrence M; Grabowski, Jonathan H; Luttbeg, Barney; Orrock, John L; Peacor, Scott D; Preisser, Evan L; Schmitz, Oswald J; Trussell, Geoffrey C

    2008-09-01

    Predator effects on prey dynamics are conventionally studied by measuring changes in prey abundance attributed to consumption by predators. We revisit four classic examples of predator-prey systems often cited in textbooks and incorporate subsequent studies of nonconsumptive effects of predators (NCE), defined as changes in prey traits (e.g., behavior, growth, development) measured on an ecological time scale. Our review revealed that NCE were integral to explaining lynx-hare population dynamics in boreal forests, cascading effects of top predators in Wisconsin lakes, and cascading effects of killer whales and sea otters on kelp forests in nearshore marine habitats. The relative roles of consumption and NCE of wolves on moose and consequent indirect effects on plant communities of Isle Royale depended on climate oscillations. Nonconsumptive effects have not been explicitly tested to explain the link between planktonic alewives and the size structure of the zooplankton, nor have they been invoked to attribute keystone predator status in intertidal communities or elsewhere. We argue that both consumption and intimidation contribute to the total effects of keystone predators, and that characteristics of keystone consumers may differ from those of predators having predominantly NCE. Nonconsumptive effects are often considered as an afterthought to explain observations inconsistent with consumption-based theory. Consequently, NCE with the same sign as consumptive effects may be overlooked, even though they can affect the magnitude, rate, or scale of a prey response to predation and can have important management or conservation implications. Nonconsumptive effects may underlie other classic paradigms in ecology, such as delayed density dependence and predator-mediated prey coexistence. Revisiting classic studies enriches our understanding of predator-prey dynamics and provides compelling rationale for ramping up efforts to consider how NCE affect traditional predator

  2. School Effectiveness Indices Revisited: Cross-Year Stability.

    ERIC Educational Resources Information Center

    Mandeville, Garrett K.

    1988-01-01

    School effectiveness indices based on residuals from regressing test performance onto prior test performance and socioeconomic status were obtained for two consecutive years for 431 elementary schools. The resulting indices were found to be stable, and it was found that grade-within-school effects dominated global school effects. (TJH)

  3. Side-effects of topical steroids: A long overdue revisit

    PubMed Central

    Coondoo, Arijit; Phiske, Meghana; Verma, Shyam; Lahiri, Koushik

    2014-01-01

    The introduction of topical steroids (TS) of varying potency have rendered the therapy of inflammatory cutaneous disorders more effective and less time-consuming. However the usefulness of these has become a double edged sword with constantly rising instances of abuse and misuse leading to serious local, systemic and psychological side effects. These side effects occur more with TS of higher potency and on particular areas of the body like face and genitalia. The article reviews the side effects of TS with special mention about peadiatric age group, also includes the measures for preventing the side effects. PMID:25396122

  4. REVISITING THE SCATTERING GREENHOUSE EFFECT OF CO{sub 2} ICE CLOUDS

    SciTech Connect

    Kitzmann, D.

    2016-02-01

    Carbon dioxide ice clouds are thought to play an important role for cold terrestrial planets with thick CO{sub 2} dominated atmospheres. Various previous studies showed that a scattering greenhouse effect by carbon dioxide ice clouds could result in a massive warming of the planetary surface. However, all of these studies only employed simplified two-stream radiative transfer schemes to describe the anisotropic scattering. Using accurate radiative transfer models with a general discrete ordinate method, this study revisits this important effect and shows that the positive climatic impact of carbon dioxide clouds was strongly overestimated in the past. The revised scattering greenhouse effect can have important implications for the early Mars, but also for planets like the early Earth or the position of the outer boundary of the habitable zone.

  5. Nanoscale effects on thermodynamics and phase equilibria in oxide systems.

    PubMed

    Navrotsky, Alexandra

    2011-08-22

    Because different solid materials (phases) have different surface energies, equilibria among them will be significantly affected by particle size. This Minireview summarizes experimental (calorimetric) data for the surface energies of oxides and discusses shifts in the stability of polymorphs, the thermodynamics of hydration, and oxidation-reduction reactions in nanoscale oxide systems.

  6. Revisit the Effect of Teaching and Learning with Technology

    ERIC Educational Resources Information Center

    Lee, Yuan-Hsuan; Waxman, Hersh; Wu, Jiun-Yu; Michko, Georgette; Lin, Grace

    2013-01-01

    We re-examined the effect of teaching and learning with technology on student cognitive and affective outcomes using the meta-analytic technique. Screening studies obtained from an electric search of databases such as PsyInfo and ERIC resulted in 58 studies (1997-2011). Overall, effect sizes were small to moderate across the cognitive and…

  7. The Use of Theory in School Effectiveness Research Revisited

    ERIC Educational Resources Information Center

    Scheerens, Jaap

    2013-01-01

    From an international review of 109 school effectiveness research studies, only 6 could be seen as theory driven. As the border between substantive conceptual models of educational effectiveness and theory-based models is not always very sharp, this number might be increased to 11 by including those studies that are based on models that make…

  8. Revisiting the Effect of Anthropomorphizing a Social Cause Campaign.

    PubMed

    Williams, Lisa A; Masser, Barbara; Sun, Jessie

    2015-01-01

    Recent research suggests that anthropomorphism can be harnessed as a tool to boost intentions to comply with social cause campaigns. Drawing on the human tendency to extend moral concern to entities portrayed as humanlike, it has been argued that adding personified features to a social campaign elevates anticipated guilt at failing to comply, and this subsequently boosts intentions to comply with that campaign. The present research aimed to extend extant research by disentangling the effects of emotional and non-emotional anthropomorphism, and differentiating amongst other emotional mechanisms of the anthropomorphism-compliance effect (namely, anticipated pride and anticipated regret). Experiment 1 (N = 294) compared the effectiveness of positive, negative, and emotionally-neutral anthropomorphized campaign posters for boosting campaign compliance intentions against non-anthropomorphized posters. We also measured potential mechanisms including anticipated guilt, regret, and pride. Results failed to support the anthropomorphism-compliance effect, and no changes in anticipated emotion according to anthropomorphism emerged. Experiments 2 (N = 150) and 3 (N = 196) represented further tests of the anthropomorphism-compliance effect. Despite high statistical power and efforts to closely replicate the conditions under which the anthropomorphism-compliance effect had been previously observed, no differences in compliance intention or anticipated emotion according to anthropomorphism emerged. A meta-analysis of the effects of anthropomorphism on compliance and anticipated emotion across the three experiments revealed effect size estimates that did not differ significantly from zero. The results of these three experiments suggest that the anthropomorphism-compliance effect is fragile and perhaps subject to contextual and idiographic influences. Thus, this research provides important insight and impetus for future research on the applied and theoretical utility of

  9. Revisiting the Effect of Anthropomorphizing a Social Cause Campaign

    PubMed Central

    Williams, Lisa A.; Masser, Barbara; Sun, Jessie

    2015-01-01

    Recent research suggests that anthropomorphism can be harnessed as a tool to boost intentions to comply with social cause campaigns. Drawing on the human tendency to extend moral concern to entities portrayed as humanlike, it has been argued that adding personified features to a social campaign elevates anticipated guilt at failing to comply, and this subsequently boosts intentions to comply with that campaign. The present research aimed to extend extant research by disentangling the effects of emotional and non-emotional anthropomorphism, and differentiating amongst other emotional mechanisms of the anthropomorphism-compliance effect (namely, anticipated pride and anticipated regret). Experiment 1 (N = 294) compared the effectiveness of positive, negative, and emotionally-neutral anthropomorphized campaign posters for boosting campaign compliance intentions against non-anthropomorphized posters. We also measured potential mechanisms including anticipated guilt, regret, and pride. Results failed to support the anthropomorphism-compliance effect, and no changes in anticipated emotion according to anthropomorphism emerged. Experiments 2 (N = 150) and 3 (N = 196) represented further tests of the anthropomorphism-compliance effect. Despite high statistical power and efforts to closely replicate the conditions under which the anthropomorphism-compliance effect had been previously observed, no differences in compliance intention or anticipated emotion according to anthropomorphism emerged. A meta-analysis of the effects of anthropomorphism on compliance and anticipated emotion across the three experiments revealed effect size estimates that did not differ significantly from zero. The results of these three experiments suggest that the anthropomorphism-compliance effect is fragile and perhaps subject to contextual and idiographic influences. Thus, this research provides important insight and impetus for future research on the applied and theoretical utility of

  10. The placebo effect revisited: lessons learned to date.

    PubMed

    Kirsch, Irving

    2013-04-01

    This article summarizes six lessons that can be learned from over a half century of scientific research on the placebo effect. These lessons are that the placebo response is not the placebo effect, it is meaningless to ask what the magnitude of the placebo effect is, it is easy to be fooled by regression artifacts, expectancy and conditioning are not conflicting processes that can be pitted against each other, some of our questions can be answered by history, and the outcomes of active treatments can be enhanced by attention to placebo components.

  11. Revisiting The Effect Of Sine Sweep Rate On Modal Identification

    NASA Astrophysics Data System (ADS)

    Roy, Nicolas; Girard, Alain

    2012-07-01

    Sine-sweep base excitation vibration tests are performed to qualify spacecraft structures in the low-frequency environment where the dynamic behavior can be characterized by a small number of modes. These modes can be extracted from the measured frequency response functions (FRF) by various modal identification methods, and then used for model validation purposes. If the sweep rate is too high, the steady-state response is not reached and the resulting FRF profile will be modified by the presence of transients. This has a direct effect on the modal parameters extracted from the FRF.Several authors have examined the effect of the sweep rate based on the response of a one-degree-of-freedom system. The goal of this paper is to adapt the approach to base-excitation vibration tests. Both increasing and decreasing exponential sweep rates are considered. The effect on the three principal modal parameters (natural frequency, damping and modal effective parameters) is examined.

  12. Dielectric effects in biopolymers: the theory of ionic saturation revisited

    SciTech Connect

    Hingerty, B.E.; Ritchie, R.H.; Ferrell, T.L.; Turner, J.E.

    1985-01-01

    Electrostatic effects are believed to determine the molecular structure and function of macromolecules in many ways. In metallo-based enzymes and in metal-macromolecule interactions in solution, these effects may predominate. In order to tackle metal ion-nucleic acid interactions theoretically, a modification of Debye's distance-dependent dielectric function first proposed more than 50 years ago is proposed. This function more closely approximates physical reality at small interatomic separations. The theory proposed here yields a dielectric function that gives reasonable agreement with experimental data in preliminary calculations. 39 references, 4 figures, 6 tables.

  13. Do Some Schools Narrow the Gap? Differential School Effectiveness Revisited

    ERIC Educational Resources Information Center

    Strand, Steve

    2016-01-01

    Relatively little research has explored whether schools differ in their effectiveness for different group of pupils (e.g. by ethnicity, poverty or gender), for different curriculum subjects (e.g. English, mathematics or science) or over time (different cohorts). This paper uses multilevel modelling to analyse the national test results at age 7 and…

  14. Modulation of additive and interactive effects by trial history revisited.

    PubMed

    Masson, Michael E J; Rabe, Maximilian M; Kliegl, Reinhold

    2017-04-01

    Masson and Kliegl (Journal of Experimental Psychology: Learning, Memory, and Cognition, 39, 898-914, 2013) reported evidence that the nature of the target stimulus on the previous trial of a lexical decision task modulates the effects of independent variables on the current trial, including additive versus interactive effects of word frequency and stimulus quality. In contrast, recent reanalyses of previously published data from experiments that, unlike the Masson and Kliegl experiments, did not include semantic priming as a factor, found no evidence for modulation of additive effects of frequency and stimulus quality by trial history (Balota, Aschenbrenner, & Yap, Journal of Experimental Psychology: Learning, Memory, and Cognition, 39, 1563-1571, 2013; O'Malley & Besner, Journal of Experimental Psychology: Learning, Memory, and Cognition, 34, 1400-1411, 2013). We report two experiments that included semantic priming as a factor and that attempted to replicate the modulatory effects found by Masson and Kliegl. In neither experiment was additivity of frequency and stimulus quality modulated by trial history, converging with the findings reported by Balota et al. and O'Malley and Besner. Other modulatory influences of trial history, however, were replicated in the new experiments and reflect potential trial-by-trial alterations in decision processes.

  15. Terminology Revisited: Effective Communications for the Agricultural Community

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Pasture-based finishing systems for meat goats, sheep and cattle are growing rapidly in the eastern USA, particularly on small farms. Increasing demand for pasture-raised meat and dairy products requires renewed efforts to communicate the best practical information as effectively as possible. Many...

  16. Second Language Comprehensibility Revisited: Investigating the Effects of Learner Background

    ERIC Educational Resources Information Center

    Crowther, Dustin; Trofimovich, Pavel; Saito, Kazuya; Isaacs, Talia

    2015-01-01

    The current study investigated first language (L1) effects on listener judgment of comprehensibility and accentedness in second language (L2) speech. The participants were 45 university-level adult speakers of English from three L1 backgrounds (Chinese, Hindi, Farsi), performing a picture narrative task. Ten native English listeners used…

  17. Revisiting the Novelty Effect: When Familiarity, Not Novelty, Enhances Memory

    ERIC Educational Resources Information Center

    Poppenk, J.; Kohler, S.; Moscovitch, M.

    2010-01-01

    Reports of superior memory for novel relative to familiar material have figured prominently in recent theories of memory. However, such "novelty effects" are incongruous with long-standing observations that familiar items are remembered better. In 2 experiments, we explored whether this discrepancy was explained by differences in the…

  18. Revisiting the Lamotrigine-Mediated Effect on Hippocampal GABAergic Transmission

    PubMed Central

    Huang, Yu-Yin; Liu, Yu-Chao; Lee, Cheng-Ta; Lin, Yen-Chu; Wang, Mong-Lien; Yang, Yi-Ping; Chang, Kaung-Yi; Chiou, Shih-Hwa

    2016-01-01

    Lamotrigine (LTG) is generally considered as a voltage-gated sodium (Nav) channel blocker. However, recent studies suggest that LTG can also serve as a hyperpolarization-activated cyclic nucleotide-gated (HCN) channel enhancer and can increase the excitability of GABAergic interneurons (INs). Perisomatic inhibitory INs, predominantly fast-spiking basket cells (BCs), powerfully inhibit granule cells (GCs) in the hippocampal dentate gyrus. Notably, BCs express abundant Nav channels and HCN channels, both of which are able to support sustained action potential generation. Using whole-cell recording in rat hippocampal slices, we investigated the net LTG effect on BC output. We showed that bath application of LTG significantly decreased the amplitude of evoked compound inhibitory postsynaptic currents (IPSCs) in GCs. In contrast, simultaneous paired recordings from BCs to GCs showed that LTG had no effect on both the amplitude and the paired-pulse ratio of the unitary IPSCs, suggesting that LTG did not affect GABA release, though it suppressed cell excitability. In line with this, LTG decreased spontaneous IPSC (sIPSC) frequency, but not miniature IPSC frequency. When re-examining the LTG effect on GABAergic transmission in the cornus ammonis region 1 (CA1) area, we found that LTG markedly inhibits both the excitability of dendrite-targeting INs in the stratum oriens and the concurrent sIPSCs recorded on their targeting pyramidal cells (PCs) without significant hyperpolarization-activated current (Ih) enhancement. In summary, LTG has no effect on augmenting Ih in GABAergic INs and does not promote GABAergic inhibitory output. The antiepileptic effect of LTG is likely through Nav channel inhibition and the suppression of global neuronal network activity. PMID:27455251

  19. IRIS Mariner 9 Data Revisited. 1; An Instrumental Effect

    NASA Technical Reports Server (NTRS)

    Formisano, V.; Grassi, D.; Piccioni, G.; Pearl, John; Bjoraker, G.; Conrath, B.; Hanel, R.

    1999-01-01

    Small spurious features are present in data from the Mariner 9 Infrared Interferometer Spectrometer (IRIS). These represent a low amplitude replication of the spectrum with a doubled wavenumber scale. This replication arises principally from an internal reflection of the interferogram at the input window. An algorithm is provided to correct for the effect, which is at the 2% level. We believe that the small error in the uncorrected spectra does not materially affect previous results; however, it may be significant for some future studies at short wavelengths. The IRIS spectra are also affected by a coding error in the original calibration that results in only positive radiances. This reduces the effectiveness of averaging spectra to improve the signal to noise ratio at small signal levels.

  20. High-dilution effects revisited. 2. Pharmacodynamic mechanisms.

    PubMed

    Bellavite, Paolo; Marzotto, Marta; Olioso, Debora; Moratti, Elisabetta; Conforti, Anita

    2014-01-01

    The pharmacodynamics aspects of homeopathic remedies are appraised by laboratory studies on the biological effects at various levels (cellular, molecular and systemic). The major question is how these medicines may work in the body. The possible answers concern the identification of biological targets, the means of drug-receptor interactions, the mechanisms of signal transmission and amplification, and the models of inversion of effects according to the traditional 'simile' rule. These problems are handled by two experimental and theoretical lines, according to the doses or dilutions considered (low-medium versus high dilutions). Homeopathic formulations in low-medium dilutions, containing molecules in the range of ultra-low doses, exploit the extreme sensitivity of biological systems to exogenous and endogenous signals. Their effects are interpreted in the framework of hormesis theories and paradoxical pharmacology. The hypotheses regarding the action mechanisms of highly diluted/dynamized solutions (beyond Avogadro-Loschmidt limit) variously invoke sensitivity to bioelectromagnetic information, participation of water chains in signalling, and regulation of bifurcation points of systemic networks. High-dilution pharmacology is emerging as a pioneering subject in the domain of nanomedicine and is providing greater plausibility to the puzzling claims of homeopathy.

  1. Stiff Spring Approximation Revisited: Inertial Effects in Nonequilibrium Trajectories.

    PubMed

    Nategholeslam, Mostafa; Gray, C G; Tomberli, Bruno

    2017-01-19

    Use of harmonic guiding potentials is the most commonly adopted method for implementing steered molecular dynamics (SMD) simulations, performed to obtain potentials of mean force (PMFs) using Jarzynski's equality and other nonequilibrium work (NEW) theorems. The stiff spring approximation (SSA) of Schulten and co-workers enables calculation of the PMF by using the work performed along many SMD trajectories in NEW theorems. We discuss and demonstrate how a high spring constant, k, required for the validity of the SSA can violate another requirement of SSA, the validity of Brownian dynamics in the system under study. These result in skewed work distributions with their width increasing with k. The skew and broadening of work distributions result in biased estimation (through invoking NEW theorems) of the PMF. Remarkably, the skewness and the broadening of work distributions are independent of the average drift velocity and physical asymmetries and can only be attributed to using too-stiff springs. We discuss the proper upper limit for k such that the inertial effects are minimized. In the presence of inertial effects, using the peak value (rather than the statistical mean) of the work distributions vastly reduces the bias in the calculated PMFs and improves the accuracy.

  2. Turbulence effects on hemolysis by revisiting experiments with LES computations

    NASA Astrophysics Data System (ADS)

    Ozturk, Mesude; O'Rear, Edgar; Papavassiliou, Dimitrios

    2015-11-01

    Determining mechanically stimulated red blood cell trauma as a function of turbulence properties is required to design prosthetic heart devices. Because blood is typically exposed to turbulence in such devices, the design of prosthetic heart devices depends on determining the effect of turbulent stresses on hemolysis. While turbulent stresses increase hemolysis when cells are exposed to them, turbulent flow characteristics in the vicinity of lysed blood cells, and the mechanism of cell damage remains uncertain. In this work, LES computations are used to investigate the effect of turbulent eddy structure on cell damage. The flow was simulated for classic Couette and capillary tube experiments, in order to examine the relation between hemolysis turbulence properties related to the dissipation of turbulent kinetic energy. The hypothesis tested is that eddies that are close in size with the erythrocytes are the ones that are responsible for hemolysis, rather than Reynolds stresses or viscous stresses. We define extensive measures, like the eddy areas for small eddies comparable to the size of the red blood cells, to provide a more general understanding of the mechanical cause of blood trauma.

  3. The Kaye effect revisited: High speed imaging of leaping shampoo

    NASA Astrophysics Data System (ADS)

    Versluis, Michel; Blom, Cock; van der Meer, Devaraj; van der Weele, Ko; Lohse, Detlef

    2003-11-01

    When a visco-elastic fluid such as shampoo or shower gel is poured onto a flat surface the fluid piles up forming a heap on which rather irregular combinations of fluid buckling, coiling and folding are observed. Under specific conditions a string of fluid leaps from the heap and forms a steady jet fed by the incoming stream. Momentum transfer of the incoming jet, combined with the shear-thinning properties of the fluid, lead to a spoon-like dimple in the highly viscous fluid pool in which the jet recoils. The jet can be stable for several seconds. This effect is known as the Kaye effect. In order to reveal its mechanism we analyzed leaping shampoo through high-speed imaging. We studied the jet formation, jet stability and jet disruption mechanisms. We measured the velocity of both the incoming and recoiled jet, which was found to be thicker and slower. By inclining the surface on which the fluid was poured we observed jets leaping at upto five times.

  4. Revisiting a pre-inflationary radiation era and its effect on the CMB power spectrum

    SciTech Connect

    Das, Suratna; Goswami, Gaurav; Rangarajan, Raghavan; Prasad, Jayanti E-mail: gaugo@prl.res.in E-mail: raghavan@prl.res.in

    2015-06-01

    We revisit the scenario where inflation is preceded by a radiation era by considering that the inflaton too could have been in thermal equilibrium early in the radiation era. Hence we take into account not only the effect of a pre-inflationary era on the inflaton mode functions but also that of a frozen thermal distribution of inflaton quanta. We initially discuss in detail the issues relevant to our scenario of a pre-inflationary radiation dominated era and then obtain the scalar power spectrum for this scenario. We find that the power spectrum is free from infrared divergences. We then use the WMAP and Planck data to determine the constraints on the inflaton comoving 'temperature' and on the duration of inflation. We find that the best fit value of the duration of inflation is less than 1 e-folding more than what is required to solve cosmological problems, while only an upper bound on the inflaton temperature can be obtained.

  5. Negative self-efficacy and goal effects revisited.

    PubMed

    Bandura, Albert; Locke, Edwin A

    2003-02-01

    The authors address the verification of the functional properties of self-efficacy beliefs and document how self-efficacy beliefs operate in concert with goal systems within a sociocognitive theory of self-regulation in contrast to the focus of control theory on discrepancy reduction. Social cognitive theory posits proactive discrepancy production by adoption of goal challenges working in concert with reactive discrepancy reduction in realizing them. Converging evidence from diverse methodological and analytic strategies verifies that perceived self-efficacy and personal goals enhance motivation and performance attainments. The large body of evidence, as evaluated by 9 meta-analyses for the effect sizes of self-efficacy beliefs and by the vast body of research on goal setting, contradicts findings (J. B. Vancouver, C. M. Thompson, & A. A. Williams, 2001; J. B. Vancouver, C. M. Thompson, E. C. Tischner, & D. J. Putka 2002) that belief in one's capabilities and personal goals is self-debilitating.

  6. Finite size effects on the QCD spectrum revisited

    SciTech Connect

    Gottlieb, S. . Dept. of Physics Brookhaven National Lab., Upton, NY )

    1992-01-01

    We have continued our study of finite size effects in the QCD spectrum on lattices ranging in size from 8[sup 3][times]24 to 16[sup 3][times]24. We have increased our statistics for quark mass am[sub q]=0.025 for the smallest lattice size. In addition, we have studied quark mass 0.01225 for lattice sizes 12[sup 3][times]24. These lattice sizes correspond to a box 1.8-3.6 fm on a side when the rho mass at zero quark mass is used to set the scale. We discuss the nucleon to rho mass ratio at a smaller value of m[pi]/m[rho] than previously studied with two dynamical flavors.

  7. Finite size effects on the QCD spectrum revisited

    SciTech Connect

    Gottlieb, S. |; MIMD Lattice Calculation Collaboration

    1992-12-31

    We have continued our study of finite size effects in the QCD spectrum on lattices ranging in size from 8{sup 3}{times}24 to 16{sup 3}{times}24. We have increased our statistics for quark mass am{sub q}=0.025 for the smallest lattice size. In addition, we have studied quark mass 0.01225 for lattice sizes 12{sup 3}{times}24. These lattice sizes correspond to a box 1.8-3.6 fm on a side when the rho mass at zero quark mass is used to set the scale. We discuss the nucleon to rho mass ratio at a smaller value of m{pi}/m{rho} than previously studied with two dynamical flavors.

  8. The serial nature of the masked onset priming effect revisited.

    PubMed

    Mousikou, Petroula; Coltheart, Max

    2014-01-01

    Reading aloud is faster when target words/nonwords are preceded by masked prime words/nonwords that share their first sound with the target (e.g., save-SINK) compared to when primes and targets are unrelated to each other (e.g., farm-SINK). This empirical phenomenon is the masked onset priming effect (MOPE) and is known to be due to serial left-to-right processing of the prime by a sublexical reading mechanism. However, the literature in this domain lacks a critical experiment. It is possible that when primes are real words their orthographic/phonological representations are activated in parallel and holistically during prime presentation, so any phoneme overlap between primes and targets (and not just initial-phoneme overlap) could facilitate target reading aloud. This is the prediction made by the only computational models of reading aloud that are able to simulate the MOPE, namely the DRC1.2.1, CDP+, and CDP++ models. We tested this prediction in the present study and found that initial-phoneme overlap (blip-BEST), but not end-phoneme overlap (flat-BEST), facilitated target reading aloud compared to no phoneme overlap (junk-BEST). These results provide support for a reading mechanism that operates serially and from left to right, yet are inconsistent with all existing computational models of single-word reading aloud.

  9. The Impenetrable Barrier Revisited - Anthroprogenic Effects on Earth's Radiation Belts

    NASA Astrophysics Data System (ADS)

    Foster, J. C.; Baker, D. N.; Erickson, P. J.; Albert, J.; Fennell, J. F.; Mishin, E. V.; Starks, M. J.; Jaynes, A. N.; Li, X.; Kanekal, S. G.; Kletzing, C.

    2015-12-01

    The Van Allen Probes are contributing significantly to the understanding of processes effecting Earth's radiation belts. It has been noted that the earthward extent of the outer zone highly-relativistic electrons encounters a nearly impenetrable barrier at a radial distance (L) near 2.8 RE inside of which they are not observed. Modeling suggests that this is the result of a balance between slow inward diffusion and hiss-induced precipitation. The large storm of 17 March 2015 afforded an excellent opportunity to investigate the impenetrable barrier using the full complement of sensors carried by the Van Allen Probes. The storm was marked by the rapid reappearance of strong fluxes of MeV electrons directly outside the barrier with the formation of very steep MeV flux gradients. In spite of the strong rapid recovery of MeV electron fluxes immediately outside the barrier, the sharpness and constancy of the gradient at the barrier is strongly suggestive of a previously unrecognized fast-acting and spatially localized mechanism responsible for the formation of such a well-defined feature during these dramatic circumstances. The Van Allen Probes regularly observe a magnetically confined bubble of VLF emissions of terrestrial origin filling the inner magnetosphere. Strongest signals are from US Navy VLF transmitters used for one-way communication to submarines. These signals largely are confined to the region of L space where their frequency is < ½ fce. The strong signal from station NAA at 24 kHz is confined to L < 2.8 where it encounters the ½ fce limit. During the event, the flux of MeV electrons decreased by 1000x across 0.5 RE outside L = 2.8 simultaneous with a 6 order of magnitude increase in the VLF wave intensity as the Probes entered the VLF bubble. The VLF transmitter frequencies are amplified at the point where they overlap natural chorus band near ½ fce suggestive of transmitter-induced triggered emissions. MeV radiation belt electrons encounter this

  10. Toward understanding the thermodynamics of TALSPEAK process. Medium effects on actinide complexation

    SciTech Connect

    Peter R Zalupski; Leigh R Martin; Ken Nash; Yoshinobu Nakamura; Masahiko Yamamoto

    2009-07-01

    The ingenious combination of lactate and diethylenetriamine-N,N,N’,N”,N”-pentaacetic acid (DTPA) as an aqueous actinide-complexing medium forms the basis of the successful separation of americium and curium from lanthanides known as the TALSPEAK process. While numerous reports in the prior literature have focused on the optimization of this solvent extraction system, considerably less attention has been devoted to the understanding of the basic thermodynamic features of the complex fluids responsible for the separation. The available thermochemical information of both lactate and DTPA protonation and metal complexation reactions are representative of the behavior of these ions under idealized conditions. Our previous studies of medium effects on lactate protonation suggest that significant departures from the speciation predicted based on reported thermodynamic values should be expected in the TALSPEAK aqueous environment. Thermodynamic parameters describing the separation chemistry of this process thus require further examination at conditions significantly removed from conventional ideal systems commonly employed in fundamental solution chemistry. Such thermodynamic characterization is the key to predictive modelling of TALSPEAK. Improved understanding will, in principle, allow process technologists to more efficiently respond to off-normal conditions during large scale process operation. In this report, the results of calorimetric and potentiometric investigations of the effects of aqueous electrolytes on the thermodynamic parameters for lactate protonation and lactate complexation of americium and neodymium will be presented. Studies on the lactate protonation equilibrium will clearly illustrate distinct thermodynamic variations between strong electrolyte aqueous systems and buffered lactate environment.

  11. Planck scale effects on the thermodynamics of photon gases

    NASA Astrophysics Data System (ADS)

    Faruk, Mir Mehedi; Rahman, Md. Muktadir

    2016-11-01

    A particular framework for quantum gravity is the doubly special relativity formalism that introduces a new observer-independent scale (the Planck scale). We resort to the methods of statistical mechanics in this framework to determine how the deformed dispersion relation affects the thermodynamics of a photon gas. The ensuing modifications to the density of states, partition function, pressure, internal energy, entropy, free energy, and specific heat are calculated. These results are compared with the outcome obtained in the Lorentz violating model of Camacho and Marcias [Gen. Relativ. Gravit. 39, 1175 (2007)]. The two types of models predict different results due to different spacetime structures near the Planck scale. The resulting modifications can be interpreted as a consequence of the deformed Lorentz symmetry present in the particular model we have considered. In the low energy limit, our calculation coincides with the usual results of photon thermodynamics in special relativity theory, in contrast to the study presented in an earlier article [Phys. Rev. D 81, 085039 (2010)].

  12. Positional and Neighboring Base Pair Effects on the Thermodynamic Stability of RNA Single Mismatches†

    PubMed Central

    Davis, Amber R.; Znosko, Brent M.

    2010-01-01

    Many naturally occurring RNA structures contain single mismatches, many of which occur near the ends of helices. However, previous thermodynamic studies have focused their efforts on thermodynamically characterizing centrally placed single mismatches. Additionally, algorithms currently used to predict secondary structure from sequence are based on two assumptions to predict stability of RNA duplexes containing this motif. It has been assumed that the thermodynamic contribution of small RNA motifs is independent of both its position in the duplex and identity of the non-nearest neighbors. Thermodynamically characterizing single mismatches three nucleotides from both the 3′ and 5′ ends (i.e., off-center) of an RNA duplex and comparing these results to those of the same single mismatch-nearest neighbor combination centrally located has allowed for the investigation of these effects. The thermodynamic contribution of 13 single mismatch-nearest neighbor combinations are reported but only 9 combinations are studied at all three duplex positions and are used to determine trends and patterns. In general, the 5′ and 3′ shifted single mismatches are relatively similar, on average, and more favorable in free energy than centrally placed single mismatches. However, close examination and comparison shows there are several associated idiosyncrasies with these identified general trends. These peculiarities may be due, in part, to the identities of the single mismatch, the nearest neighbors, and the non-nearest neighbors, along with the effects of single mismatch position in the duplex. The prediction algorithm recently proposed by Davis and Znosko (Biochemistry 47, 10178–10187) is used to predict the thermodynamic parameters of single mismatch contribution and is compared to the measured values presented here. This comparison suggests the proposed model is a good approximation but could be improved by the addition of parameters which account for positional and/or non

  13. Dynamical, thermodynamical and hydrological effects of the third pole (Invited)

    NASA Astrophysics Data System (ADS)

    Webster, P. J.

    2013-12-01

    The Himalayan-Tibetan Plateau (HTP) can be described as a mechanical barrier and a thermodynamical heat source or combinations of both affects, during both the summer and the winter, and, particularly during transitions seasons. The upper troposphere above the HTP is anomalously moister and warmer than any other tropical and subtropical land mass. The HTP is the source of almost all major Asian rivers and snow-melt is a major component of fresh water for a large percentage of the world's population. We examine the exceptional physics of thermal and mechanical forcing associated with the HTP and compare them with forcing occurring at similar latitudes in other locations especially Africa and Australia. We also examine how the forcing from the HTP may change in a warming world especially with respect to the vigor of the South Asian monsoon and fresh water availability. Noting that other monsoon regions were more vigorous during the hypsithermal of the Holocene, we attempt to determine changes that may occur in a warmer world.

  14. Dynamics and thermodynamics of a tornado: Rotation effects

    NASA Astrophysics Data System (ADS)

    Ben-Amots, N.

    2016-09-01

    This paper investigates the relevant processes in the tornado including the dynamics of rotation and thermodynamics as well as condensation. The main novelty of this paper is the explanation of the phenomena occurring in the central downflow. The reduced pressure in the tornado's funnel sucks air and water vapor from the cloud above the tornado. The latent heat of condensation is released in the funnel. The centrifugal force drives the generated water drops out of the funnel. The latent heat of condensation released is also transferred out of the funnel, and supplies the helically ascending air flow surrounding the tornado with additional buoyancy energy. This process gives the tornado increased strength compared to the dust devil type of flow, thus explaining why tornadoes occur always under a cloud, and why the tornado pipe can reach a height of a kilometer and more. To sustain a tornado, the temperature of water vapor at the cloud's base should be higher than the surroundings by a certain minimal value. Remote infrared temperature measurements of clouds' bases may provide indications of the probability that a cloud can spawn a tornado, which may increase the lead time.

  15. Effects from switching on PIC simulations: Geospace Environmental Modeling (GEM) reconnection setup revisited

    NASA Astrophysics Data System (ADS)

    Bourdin, P. A.; Nakamura, T.; Narita, Y.

    2015-12-01

    Electromagnetic Parcile-In-Cell (PIC) simulations are widely used to study plasma phenomena where kinetic scales are coupled to fluid scales. One of these phenomena is the evolution of magnetic reconnection. Switch-on effects have been described earlier for magneto-/hydrodynamic (MHD and HD) simulations, where oscillations are ignited by the initial condition and the usual instantaneous way of starting a simulation run. Here we revisit the GEM setup (a Harris current sheet) and demonstrate the immediate generation of oscillations propagating perpendicular to the magnetic shear layer (in Bz). Also we show how these oscillations do not dissipate quickly and will later be mode-converted to generate wave power, first in By, much later also in Bx (pointing along the shear direction). One needs to take care not to interpret these oscillations as physical wave modes associated with the nature of reconnection. We propose a method to prevent such switch-on effects from the beginning, that should be considered for implementation in other PIC simulation codes as well.

  16. Revisiting the monopole components of effective interactions for the shell model

    NASA Astrophysics Data System (ADS)

    Wang, X. B.; Dong, G. X.

    2015-12-01

    In this paper, we revisit the monopole components of effective interactions for the shell model. Without going through specific nuclei or shell gaps, universal roles of central, tensor, and spin-orbit forces can be proved, reflecting the intrinsic features of shell model effective interactions. For monopole matrix elements, even and odd channels of central force often have a canceling effect. However, for the contributions to the shell evolution, its even and odd channels could have both positive or negative contributions, enhancing the role of central force on the shell structure. Tensor force is generally weaker than central force. However, for the effect on shell evolutions, tensor force can dominate or play a competitive role. A different systematics has been discovered between T = 1 and 0 channels. For example, tensor force, well established in the T = 0 channel, becomes uncertain in the T = 1 channel. We calculate the properties of neutron-rich oxygen and calcium isotopes in order to study T = 1 channel interactions further. It is learned that the main improvements of empirical interactions are traced to the central force. For non-central forces, antisymmetric spin-orbit (ALS) force, originated from many-body perturbations or three-body force, could also play an explicit role. T = 1 tensor forces are less constrained so their effect can differ in different empirical interactions. The influence of tensor force may sometimes be canceled by many-body effects. For T = 0 channels of effective interactions, which is the main source of neutron-proton correlations, central and tensor forces are the leading components. For T = 1 channels, which can act between like-particles, the request for many-body correlations could be more demanding, so that the monopole anomaly of the T = 1 channel might be more serious.

  17. Thermodynamic and functional characteristics of deep-sea enzymes revealed by pressure effects.

    PubMed

    Ohmae, Eiji; Miyashita, Yurina; Kato, Chiaki

    2013-09-01

    Hydrostatic pressure analysis is an ideal approach for studying protein dynamics and hydration. The development of full ocean depth submersibles and high pressure biological techniques allows us to investigate enzymes from deep-sea organisms at the molecular level. The aim of this review was to overview the thermodynamic and functional characteristics of deep-sea enzymes as revealed by pressure axis analysis after giving a brief introduction to the thermodynamic principles underlying the effects of pressure on the structural stability and function of enzymes.

  18. Effects of precipitation on the thermodynamic structure of the trade wind boundary layer

    NASA Technical Reports Server (NTRS)

    Albrecht, Bruce A.

    1993-01-01

    A model of the thermodynamic structure of the trade wind boundary layer is formulated to include the parameterization of precipitation in relatively shallow clouds. Although the area-averaged simulated precipitation rates are relatively small (less than 1 mm/day), the inclusion of precipitation has an appreciable effect on the predicted thermodynamic structure. The cloud layer structure simulated with precipitation is warmer, drier, and more stable than that simulated without precipitation. The simulated inversion height is lowered by as much as 60 mbar when precipitation is included.

  19. Thermodynamic network model for predicting effects of substrate addition and other perturbations on subsurface microbial communities

    SciTech Connect

    Jack Istok; Melora Park; James McKinley; Chongxuan Liu; Lee Krumholz; Anne Spain; Aaron Peacock; Brett Baldwin

    2007-04-19

    The overall goal of this project is to develop and test a thermodynamic network model for predicting the effects of substrate additions and environmental perturbations on microbial growth, community composition and system geochemistry. The hypothesis is that a thermodynamic analysis of the energy-yielding growth reactions performed by defined groups of microorganisms can be used to make quantitative and testable predictions of the change in microbial community composition that will occur when a substrate is added to the subsurface or when environmental conditions change.

  20. High pressure effects revisited for the cuprate superconductor family with highest critical temperature

    PubMed Central

    Yamamoto, Ayako; Takeshita, Nao; Terakura, Chieko; Tokura, Yoshinori

    2015-01-01

    How to enhance the superconducting critical temperature (Tc) has been a primary issue since the discovery of superconductivity. The highest Tc reported so far is 166 K in HgBa2Ca2Cu3O8+δ (Hg1223) at high pressure of 23 GPa, as determined with the reduction onset, but not zero, of resistivity. To clarify the possible condition of the real maximum Tc, it is worth revisiting the effects of pressure on Tc in the highest Tc family. Here we report a systematic study of the pressure dependence of Tc in HgBa2CaCu2O6+δ (Hg1212) and Hg1223 with the doping level from underdoped to overdoped. The Tc with zero resistivity is probed with a cubic-anvil-type apparatus that can produce hydrostatic pressures. Variation, not only increase but also decrease, of Tc in Hg1212 and Hg1223 with pressure strongly depends on the initial doping levels. In particular, we confirm a maximum Tc of 153 K at 22 GPa in slightly underdoped Hg1223. PMID:26619829

  1. Effect of temperature on microbial growth rate - thermodynamic analysis, the arrhenius and eyring-polanyi connection

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The objective of this work is to develop a new thermodynamic mathematical model for evaluating the effect of temperature on the rate of microbial growth. The new mathematical model is derived by combining the Arrhenius equation and the Eyring-Polanyi transition theory. The new model, suitable for ...

  2. Thermodynamic method of calculating the effect of alloying additives on interphase interaction in composite materials

    NASA Technical Reports Server (NTRS)

    Tuchinsky, L. I.

    1986-01-01

    The effect of alloying additives to the matrix of a composite on the high temperature solubility rate of a single component fiber was analyzed thermodynamically. With an example of binary Ni alloys, with Group IV-VI transition metals reinforced with W fibers, agreement between the calculated and experimental data was demonstrated.

  3. Student Oriented Approaches in the Teaching of Thermodynamics at Universities--Developing an Effective Course Structure

    ERIC Educational Resources Information Center

    Partanen, Lauri

    2016-01-01

    The aim of this study was to apply current pedagogical research in order to develop an effective course and exercise structure for a physical chemistry thermodynamics course intended for second or third year university students of chemistry. A mixed-method approach was used to measure the impact the changes had on student learning. In its final…

  4. Effects of critical fluctuations on the thermodynamic properties of fluids and fluid mixtures

    NASA Astrophysics Data System (ADS)

    Jin, Guo-Xiong

    In fluids and fluid mixtures, the effects of critical fluctuations remain significant in a very large region of temperatures and densities. Asymptotically close to the critical point, these effects can be described by the scaling theory. However, the asymptotic region is usually extremely small. This thesis presents a crossover formalism to deal with the complete effects of the critical fluctuations on the thermodynamic properties of fluids and fluid mixtures. Continuing the work of Nicoll and Albright and Chen et al., we propose an approximate crossover solution of the renormalization-group equation, which accounts for the critical fluctuations. This solution provides us with a procedure to construct a thermodynamic free energy that reproduces the singular behavior near the critical point and incorporates the crossover from singular critical behavior to regular mean-fleld behavior of one-component fluids. This procedure is then extended to binary fluid mixtures near the vapor-liquid critical line. The resulting thermodynamic free energy for mixtures yields an accurate description of the thermodynamic properties of mixtures of carbon dioxide and ethane. The renormalization of the critical exponents in these mixtures is also analyzed in detail. Finally, a crossover theory in closed form is constructed, which connects the universal critical behavior with the universal ideal-gas behavior at low densities.

  5. Thermodynamics of small systems embedded in a reservoir: a detailed analysis of finite size effects

    NASA Astrophysics Data System (ADS)

    Schnell, Sondre K.; Vlugt, Thijs J. H.; Simon, Jean-Marc; Bedeaux, Dick; Kjelstrup, Signe

    2012-06-01

    We present a detailed study on the finite size scaling behaviour of thermodynamic properties for small systems of particles embedded in a reservoir. Previously, we derived that the leading finite size effects of thermodynamic properties for small systems scale with the inverse of the linear length of the small system, and we showed how this can be used to describe systems in the thermodynamic limit [Chem. Phys. Lett. 504, 199 (2011)]. This approach takes into account an effective surface energy, as a result of the non-periodic boundaries of the small embedded system. Deviations from the linear behaviour occur when the small system becomes very small, i.e. smaller than three times the particle diameter in each direction. At this scale, so-called nook- and corner effects will become important. In this work, we present a detailed analysis to explain this behaviour. In addition, we present a model for the finite size scaling when the size of the small system is of the same order of magnitude as the reservoir. The developed theory is validated using molecular simulations of systems containing Lennard-Jones and WCA particles, and leads to significant improvements over our previous approach. Our approach eventually leads to an efficient method to compute the thermodynamic factor of macroscopic systems from finite size scaling, which is for example required for converting Fick and Maxwell-Stefan transport diffusivities.

  6. Thermodynamics of multicaloric effects in multiferroic materials: application to metamagnetic shape-memory alloys and ferrotoroidics

    SciTech Connect

    Planes, Antoni; Castán, Teresa; Saxena, Avadh

    2016-07-11

    In this paper, we develop a general thermodynamic framework to investigate multicaloric effects in multiferroic materials. This is applied to the study of both magnetostructural and magnetoelectric multiferroics. Landau models with appropriate interplay between the corresponding ferroic properties (order parameters) are proposed for metamagnetic shape-memory and ferrotoroidic materials, which, respectively, belong to the two classes of multiferroics. For each ferroic property, caloric effects are quantified by the isothermal entropy change induced by the application of the corresponding thermodynamically conjugated field. The multicaloric effect is obtained as a function of the two relevant applied fields in each class of multiferroics. It is further shown that multicaloric effects comprise the corresponding contributions from caloric effects associated with each ferroic property and the cross-contribution arising from the interplay between these ferroic properties. Finally, this article is part of the themed issue ‘Taking the temperature of phase transitions in cool materials’.

  7. Thermodynamics of multicaloric effects in multiferroic materials: application to metamagnetic shape-memory alloys and ferrotoroidics

    DOE PAGES

    Planes, Antoni; Castán, Teresa; Saxena, Avadh

    2016-07-11

    In this paper, we develop a general thermodynamic framework to investigate multicaloric effects in multiferroic materials. This is applied to the study of both magnetostructural and magnetoelectric multiferroics. Landau models with appropriate interplay between the corresponding ferroic properties (order parameters) are proposed for metamagnetic shape-memory and ferrotoroidic materials, which, respectively, belong to the two classes of multiferroics. For each ferroic property, caloric effects are quantified by the isothermal entropy change induced by the application of the corresponding thermodynamically conjugated field. The multicaloric effect is obtained as a function of the two relevant applied fields in each class of multiferroics. Itmore » is further shown that multicaloric effects comprise the corresponding contributions from caloric effects associated with each ferroic property and the cross-contribution arising from the interplay between these ferroic properties. Finally, this article is part of the themed issue ‘Taking the temperature of phase transitions in cool materials’.« less

  8. Thermodynamics of multicaloric effects in multiferroic materials: application to metamagnetic shape-memory alloys and ferrotoroidics.

    PubMed

    Planes, Antoni; Castán, Teresa; Saxena, Avadh

    2016-08-13

    We develop a general thermodynamic framework to investigate multicaloric effects in multiferroic materials. This is applied to the study of both magnetostructural and magnetoelectric multiferroics. Landau models with appropriate interplay between the corresponding ferroic properties (order parameters) are proposed for metamagnetic shape-memory and ferrotoroidic materials, which, respectively, belong to the two classes of multiferroics. For each ferroic property, caloric effects are quantified by the isothermal entropy change induced by the application of the corresponding thermodynamically conjugated field. The multicaloric effect is obtained as a function of the two relevant applied fields in each class of multiferroics. It is further shown that multicaloric effects comprise the corresponding contributions from caloric effects associated with each ferroic property and the cross-contribution arising from the interplay between these ferroic properties.This article is part of the themed issue 'Taking the temperature of phase transitions in cool materials'.

  9. Effects of interaction on thermodynamics of a repulsive Bose-Einstein condensate

    NASA Astrophysics Data System (ADS)

    Bhattacharyya, Satadal; Das, Tapan Kumar; Chakrabarti, Barnali

    2013-11-01

    We report the effects of interaction on thermodynamic properties of a repulsive Bose-Einstein condensate confined in a harmonic trap by using the correlated potential harmonics expansion method. This many-body technique permits the use of a realistic interactomic interaction, which gives rise to the effective long-range interaction of the condensate in terms of the s-wave scattering length. We have computed temperature (T) dependence of the chemical potential, specific heat, condensate fraction, entropy, pressure, and the average energy per particle of a system containing a large number (A) of 87Rb atoms in the Joint Institute for Laboratory Astrophysics (JILA) trap. The repulsion among the interacting bosons results in a small but measurable drop of condensate fraction and critical temperature (Tc), compared to those of a noninteracting condensate. These are in agreement with the experiment. Although all thermodynamic quantities have a strong dependence on A and to a smaller extent on the interatomic interaction, our numerical calculation appears to show that a thermodynamic quantity per particle follows a universal behavior as a function of T/Tc. This shows the importance of Tc for all thermodynamic properties of the condensate. As expected, for T>Tc, these properties follow those of a trapped noncondensed Bose gas.

  10. Lakatos Revisited.

    ERIC Educational Resources Information Center

    Court, Deborah

    1999-01-01

    Revisits and reviews Imre Lakatos' ideas on "Falsification and the Methodology of Scientific Research Programmes." Suggests that Lakatos' framework offers an insightful way of looking at the relationship between theory and research that is relevant not only for evaluating research programs in theoretical physics, but in the social…

  11. Substituent effect on the thermodynamic solubility of structural analogs: relative contribution of crystal packing and hydration.

    PubMed

    Ozaki, Shunsuke; Nakagawa, Yoshiaki; Shirai, Osamu; Kano, Kenji

    2014-11-01

    Thermodynamic analysis of the solubility of benzoylphenylurea (BPU) derivatives was conducted to investigate the relative importance of crystal packing and hydration for improving solubility with minor structural modification. The contribution of crystal packing to solubility was evaluated from the change in Gibbs energy on the transition from the crystalline to liquid state. Hydration Gibbs energy was estimated using a linear free-energy relationship between octanol-water partition coefficients and gas-water partition coefficients. The established solubility model satisfactorily explained the relative thermodynamic solubility of the model compounds and revealed that crystal packing and hydration equally controlled solubility of the structural analogs. All hydrophobic substituents were undesirable for solubility in terms of hydration, as expected. On the other hand, some of these hydrophobic substituents destabilized crystal packing and improved the solubility of the BPU derivatives when their impact on crystal packing exceeded their negative influence on hydration. The replacement of a single substituent could cause more than a 10-fold enhancement in thermodynamic solubility; this degree of improvement was comparable to that generally achieved by amorphous formulations. Detailed analysis of thermodynamic solubility will allow us to better understand the true substituent effect and design drug-like candidates efficiently.

  12. The effect of citric acid on the activity, thermodynamics and conformation of mushroom polyphenoloxidase.

    PubMed

    Liu, Wei; Zou, Li-qiang; Liu, Jun-ping; Zhang, Zhao-qin; Liu, Cheng-mei; Liang, Rui-hong

    2013-09-01

    Few reports have focused on the effect of citric acid on thermodynamics and conformation of polyphenoloxidase (PPO). In this study, variations on activity, thermodynamics and conformation of mushroom PPO induced by citric acid (1-60mM) and relationships among these were investigated. It showed that with the increasing concentration of citric acid, the activity of PPO decreased gradually to an inactivity condition; inactivation rate constant (k) of PPO increased and the activation energy (Ea) as well as thermodynamic parameters (ΔG, ΔH, ΔS) decreased, which indicated that the thermosensitivity, stability and number of non-covalent bonds of PPO decreased. The conformation was gradually unfolded, which was reflected in the decrease of α-helix contents, increase of β-sheet and exposure of aromatic amino acid residuals. Moreover, two linear relationships of relative activities, enthalpies (ΔH) against α-helix contents were obtained. It indicated that changes of activity and thermodynamics might correlate to the unfolding of conformation.

  13. Size and shape effects on the thermodynamic properties of nanoscale volumes of water.

    PubMed

    Strøm, Bjørn A; Simon, Jean-Marc; Schnell, Sondre K; Kjelstrup, Signe; He, Jianying; Bedeaux, Dick

    2017-03-17

    Small systems are known to deviate from the classical thermodynamic description, among other things due to their large surface area to volume ratio compared to corresponding big systems. As a consequence, extensive thermodynamic properties are no longer proportional to the volume, but are instead higher order functions of size and shape. We investigate such functions for second moments of probability distributions of fluctuating properties in the grand-canonical ensemble, focusing specifically on the volume and surface terms of Hadwiger's theorem, explained in Klain, Mathematika, 1995, 42, 329-339. We resolve the shape dependence of the surface term and show, using Hill's nanothermodynamics [Hill, J. Chem. Phys., 1962, 36, 3182], that the surface satisfies the thermodynamics of a flat surface as described by Gibbs [Gibbs, The Scientific Papers of J. Willard Gibbs, Volume 1, Thermodynamics, Ox Bow Press, Woodbridge, Connecticut, 1993]. The Small System Method (SSM), first derived by Schnell et al. [Schnell et al., J. Phys. Chem. B, 2011, 115, 10911], is extended and used to analyze simulation data on small systems of water. We simulate water as an example to illustrate the method, using TIP4P/2005 and other models, and compute the isothermal compressibility and thermodynamic factor. We are able to retrieve the experimental value of the bulk phase compressibility within 2%, and show that the compressibility of nanosized volumes increases by up to a factor of two as the number of molecules in the volume decreases. The value for a tetrahedron, cube, sphere, polygon, etc. can be predicted from the same scaling law, as long as second order effects (nook and corner effects) are negligible. Lastly, we propose a general formula for finite reservoir correction to fluctuations in subvolumes.

  14. Effects of surfactants and thermodynamic activity of model active ingredient on transport over plant leaf cuticle.

    PubMed

    Fagerström, Anton; Kocherbitov, Vitaly; Ruzgas, Tautgirdas; Westbye, Peter; Bergström, Karin; Engblom, Johan

    2013-03-01

    The main objective of this study was to investigate the mechanism of molecular transport across the cuticle of Clivia leaves. In vitro diffusion methodology was used to investigate the transport of a systemic fungicide, tebuconazole, over a model silicone membrane, enzymatically isolated cuticle membranes, and dermatomed leaves. It was shown that dermatomed leaves may replace enzymatically isolated cuticles. Furthermore, the effects of two surfactants, C(10)EO(7) and C(8)G(1.6), on the fungicide transport were investigated. Tebuconazole cuticle permeation was described using Fick's first law of diffusion, expressed by the thermodynamic activity of the solute in the membrane. A new method for calculation of diffusion coefficients in the membrane is proposed. To access the thermodynamic activity of the fungicide in the membranes, sorption isotherms of tebuconazole in the membrane materials studied were recorded. The thermodynamic activity of the fungicide in aqueous solutions was calculated from solubility data. For that purpose, the effect of surfactants on tebuconazole solubility was studied. The results show that addition of surfactants allows for higher concentrations of tebuconazole available for penetration. Nonetheless, at a fixed fungicide thermodynamic activity, all formulations produced the same flux over the silicone membrane independently on the fungicide concentration. This shows that the driving force across non-responding membranes is the gradient of thermodynamic activity, rather than the gradient of the fungicide concentration. In case of leaves, surfactants induced the same quantitative increase in both flux and diffusion coefficient of solute in the cuticle, while the cuticle-water partition coefficient was unaffected.

  15. Effects of quantum gravity on the inflationary parameters and thermodynamics of the early universe

    NASA Astrophysics Data System (ADS)

    Tawfik, A.; Magdy, H.; Farag Ali, Ahmed

    2013-06-01

    The effects of generalized uncertainty principle (GUP) on the inflationary dynamics and the thermodynamics of the early universe are studied. Using the GUP approach, the tensorial and scalar density fluctuations in the inflation era are evaluated and compared with the standard case. We find a good agreement with the Wilkinson Microwave Anisotropy Probe data. Assuming that a quantum gas of scalar particles is confined within a thin layer near the apparent horizon of the Friedmann-Lemaitre-Robertson-Walker universe which satisfies the boundary condition, the number and entropy densities and the free energy arising form the quantum states are calculated using the GUP approach. A qualitative estimation for effects of the quantum gravity on all these thermodynamic quantities is introduced.

  16. Thermodynamic effect of the ion sound instability in the ionosphere

    SciTech Connect

    Khazanov, G.V.; Gombosi, T.I.; Gorbachev, O.A.

    1994-04-01

    During geomagnetic disturbances when the ring current interacts intensely with the plasmasphere, the plasma of this region undergoes a strong heating due to an ion cyclotron instability. This is followed by the transfer of heat along geomagnetic field lines from the heating region to the ionosphere. One of the results of this process is the formation of a non isothermal region (in which T{sub e}>3.4 T{sub i} at ionospheric heights) caused by a rapid cooling the H{sup +} ions due to their resonant charge exchange with neutral hydrogen. Heat transfer from the top of the flux tube to the ionosphere is investigated using a hydrodynamic model for the ionosphere-plasmasphere coupling. Field-aligned currents, present in the topside ionosphere, are often accompanied by ion sound turbulence. The turbulence scatters electrons, increasing the total electron collision frequency through wave-particle effects. The influence of wave-particle interactions introduces an anomalous component to the total collision frequency, which modifies substantially the heat conduction coefficient of the plasma. As a result, the plasma is heated more intensely above than below this region of ion sound turbulence. 33 refs., 3 figs.

  17. Thermodynamic effect of the ion sound instability in the ionosphere

    NASA Technical Reports Server (NTRS)

    Khazanov, G. V.; Gombosi, T. I.; Gorbachev, O. A.; Trukhan, A. A.; Miller, R. H.

    1994-01-01

    During geomagnetic disturbances when the ring current interacts intensely with the plasmasphere, the plasma of this region undergoes a strong heating due to an ion cyclotron instability. This is followed by the transfer of heat along geomagnetic field lines from the heating region to the ionosphere. One of the results of this process is the formation of non-isothermal region (in which T(sub e) greater than 3.4 T(sub i) at ionospheric heights) caused by a rapid cooling the H(+) ions due to their resonant charge exchange with neutral hydrogen. Heat transfer from the top of the flux tube to the ionosphere is investigated using a hydrodynamic model for the ionosphere-plasmasphere coupling. Field-aligned currents, present in the topside ionosphere, are often accompanied by ion sound turbulence. The turbulence scatters electrons, increasing the total electron collision frequency through wave-particle effects. The influence of wave-particle interactions introduces an anomalous component to the total collision frequency, which modifies substantially the heat conduction coefficient of the plasma. As a result, the plasma is heated more intensely above than below this region of ion sound turbulence.

  18. A thermodynamic treatment of partially saturated soils revealing the structure of effective stress

    NASA Astrophysics Data System (ADS)

    Jiang, Yimin; Einav, Itai; Liu, Mario

    2017-03-01

    A rigorous thermodynamic treatment of partially saturated soils is developed using a minimal number of assumptions. The derivation is carried out in a way that does not require to explicitly track the complex shapes of interfaces between the solid, fluid and gas domains. Instead, suction is the property being recovered explicitly through the minimisation of energy around an ideal 'suctionless limit', while considering the different compressibilities of the three domains. In interpreting experimental data the derivation ensures the thermodynamic equilibrium between the chemical potentials of the soil and measurement cells, while carefully distinguishing intrinsic from measured pressures and suctions. A most general expression for the effective stress of partially saturated soils is then derived that is strictly linked to the soil-water retention curve (SWRC). The structure of the effective stress broadly depends on the three thermodynamic densities characterising the solid, liquid and gas domains. Special cases of SWRC are explored, which reveals conditions for which the structure of the effective stress may agree with previously proposed empirical relationships.

  19. Thermodynamic properties of the blackbody radiation: A Kaniadakis approach

    NASA Astrophysics Data System (ADS)

    Lourek, Imene; Tribeche, Mouloud

    2017-02-01

    The thermodynamic properties of the blackbody radiation are revisited, for the first time, within the theoretical framework of the κ-statistics introduced by Kaniadakis. Using the κ-counterpart of the Bose-Einstein distribution, generalized expressions for the free energy, the entropy, the specific heat, and the pressure are obtained. All quantities are shown to recover their standard expressions in the limit κ → 0. The reexamination of the thermodynamic properties of the blackbody radiation shows that it emits more energy with an increase of the value of | κ | in comparison with the standard Planck radiation law. Moreover, the effects of the deformed Kaniadakis statistics are shown to be more appreciable for high temperatures. Our results could be used as a theoretical support for experimental studies implying blackbody radiation such as the study of microwave background radiation.

  20. Thermodynamic analysis and experimental study of the effect of atmospheric pressure on the ice point

    SciTech Connect

    Harvey, A. H.; McLinden, M. O.; Tew, W. L.

    2013-09-11

    We present a detailed thermodynamic analysis of the temperature of the ice point as a function of atmospheric pressure. This analysis makes use of accurate international standards for the properties of water and ice, and of available high-accuracy data for the Henry's constants of atmospheric gases in liquid water. The result is an ice point of 273.150 019(5) K at standard atmospheric pressure, with higher ice-point temperatures (varying nearly linearly with pressure) at lower pressures. The effect of varying ambient CO{sub 2} concentration is analyzed and found to be significant in comparison to other uncertainties in the model. The thermodynamic analysis is compared with experimental measurements of the temperature difference between the ice point and the triple point of water performed at elevations ranging from 145 m to 4302 m, with atmospheric pressures from 101 kPa to 60 kPa.

  1. Fluorination effects on the thermodynamic, thermophysical and surface properties of ionic liquids

    PubMed Central

    Reis, P. M.; Carvalho, P. J.; Lopes-da-Silva, J. A.; Esperança, J. M. S. S.; Araújo, J. M. M.; Rebelo, L. P. N.; Freire, M. G.; Pereiro, A. B.

    2016-01-01

    This paper reports the thermal, thermodynamic, thermophysical and surface properties of eight ionic liquids with fluorinated alkyl side chain lengths equal or greater than four carbon atoms. Melting and decomposition temperatures were determined together with experimental densities, surface tensions, refractive indices, dynamic viscosities and ionic conductivities in a temperature interval ranging from 293.15 to 353.15 K. The surface properties of these fluorinated ionic liquids were discussed and several thermodynamic functions, as well as critical temperatures, were estimated. Coefficients of isobaric thermal expansion, molecular volumes and free volume effects were calculated from experimental values of density and refractive index and compared with previous data. Finally, Walden plots were used to evaluate the ionicity of the investigated ionic liquids. PMID:27642190

  2. Thermodynamics at the microscale: from effective heating to the Brownian Carnot engine

    NASA Astrophysics Data System (ADS)

    Dinis, L.; Martínez, I. A.; Roldán, É.; Parrondo, J. M. R.; Rica, R. A.

    2016-05-01

    We review a series of experimental studies of the thermodynamics of nonequilibrium processes at the microscale. In particular, in these experiments we studied the fluctuations of the thermodynamic properties of a single optically-trapped microparticle immersed in water and in the presence of external random forces. In equilibrium, the fluctuations of the position of the particle can be described by an effective temperature that can be tuned up to thousands of Kelvin. Isothermal and non-isothermal thermodynamic processes that also involve changes in a control parameter were implemented by controlling the effective temperature of the particle and the stiffness of the optical trap. Since truly adiabatic processes are unfeasible in colloidal systems, mean adiabatic protocols where no average heat is exchanged between the particle and the environment are discussed and implemented. By concatenating isothermal and adiabatic protocols, it is shown how a single-particle Carnot engine can be constructed. Finally, we provide an in-depth study of the fluctuations of the energetics and the efficiency of the cycle.

  3. Association effects in pure methanol via Monte Carlo simulations. II. Thermodynamics

    NASA Astrophysics Data System (ADS)

    Gómez-Álvarez, Paula; Romaní, Luis; González-Salgado, Diego

    2013-01-01

    A simple methodology [P. Gómez-Álvarez, A. Dopazo-Paz, L. Romani, and D. González-Salgado, J. Chem. Phys. 134, 014512 (2011), 10.1063/1.3524201] recently developed in the light of the Monte Carlo molecular simulation technique was used in this work to study the association effects on the response functions of methanol over the whole thermodynamic state space. It consists basically on evaluating the first order properties of the fluid (energy and volume) in terms of those for two hypothetical fluids living in the bulk composed by monomers and associated molecules, respectively. In this context, the second order thermodynamic derivatives can be expressed in a perturbative way as the sum of the monomer term (reference term) and the association contribution. Specifically, both contributions to the residual isobaric heat capacity, and to the pressure and temperature derivatives of the volume were determined for the optimized potential for liquid simulation (OPLS) of methanol through NPT Monte Carlo simulations from 250 K to 1000 K along the supercritical isobars 25, 100, 200, 500 MPa, and from 800 K to 350 K at 0.1 MPa. Results showed that both terms are relevant for the residual isobaric heat capacity and that their influence depends considerably on the thermodynamic conditions; however, the volumetric response functions were found mainly affected by the monomer contribution, especially the pressure derivative of the volume.

  4. Understanding the Thermodynamic Properties of the Elastocaloric Effect Through Experimentation and Modelling

    NASA Astrophysics Data System (ADS)

    Tušek, Jaka; Engelbrecht, Kurt; Mañosa, Lluis; Vives, Eduard; Pryds, Nini

    2016-12-01

    This paper presents direct and indirect methods for studying the elastocaloric effect (eCE) in shape memory materials and its comparison. The eCE can be characterized by the adiabatic temperature change or the isothermal entropy change (both as a function of applied stress/strain). To get these quantities, the evaluation of the eCE can be done using either direct methods, where one measures (adiabatic) temperature changes or indirect methods where one can measure the stress-strain-temperature characteristics of the materials and from these deduce the adiabatic temperature and isothermal entropy changes. The former can be done using the basic thermodynamic relations, i.e. Maxwell relation and Clausius-Clapeyron equation. This paper further presents basic thermodynamic properties of shape memory materials, such as the adiabatic temperature change, isothermal entropy change and total entropy-temperature diagrams (all as a function of temperature and applied stress/strain) of two groups of materials (Ni-Ti and Cu-Zn-Al alloys) obtained using indirect methods through phenomenological modelling and Maxwell relation. In the last part of the paper, the basic definition of the efficiency of the elastocaloric thermodynamic cycle (coefficient of performance) is defined and discussed.

  5. Association effects in pure methanol via Monte Carlo simulations. II. Thermodynamics.

    PubMed

    Gómez-Álvarez, Paula; Romaní, Luis; González-Salgado, Diego

    2013-01-28

    A simple methodology [P. Gómez-Álvarez, A. Dopazo-Paz, L. Romani, and D. González-Salgado, J. Chem. Phys. 134, 014512 (2011)] recently developed in the light of the Monte Carlo molecular simulation technique was used in this work to study the association effects on the response functions of methanol over the whole thermodynamic state space. It consists basically on evaluating the first order properties of the fluid (energy and volume) in terms of those for two hypothetical fluids living in the bulk composed by monomers and associated molecules, respectively. In this context, the second order thermodynamic derivatives can be expressed in a perturbative way as the sum of the monomer term (reference term) and the association contribution. Specifically, both contributions to the residual isobaric heat capacity, and to the pressure and temperature derivatives of the volume were determined for the optimized potential for liquid simulation (OPLS) of methanol through NPT Monte Carlo simulations from 250 K to 1000 K along the supercritical isobars 25, 100, 200, 500 MPa, and from 800 K to 350 K at 0.1 MPa. Results showed that both terms are relevant for the residual isobaric heat capacity and that their influence depends considerably on the thermodynamic conditions; however, the volumetric response functions were found mainly affected by the monomer contribution, especially the pressure derivative of the volume.

  6. Thermodynamic laws and consistent Eulerian formulation of finite elastoplasticity with thermal effects

    NASA Astrophysics Data System (ADS)

    Xiao, Heng; Bruhns, Otto T.; Meyers, Albert

    2007-02-01

    Recently it has been demonstrated that, on the basis of the separation D=De+Dp arising from the split of the stress power and two consistency criteria for objective Eulerian rate formulations, it is possible to establish a consistent Eulerian rate formulation of finite elastoplasticity in terms of the Kirchhoff stress and the stretching, without involving additional deformation-like variables labelled "elastic" or "plastic". It has further been demonstrated that this consistent formulation leads to a simple essential structure implied by the work postulate, namely, both the normality rule for plastic flow Dp and the convexity of the yield surface in Kirchhoff stress space. Here, we attempt to place such an Eulerian formulation on the thermodynamic grounds by extending it to a general case with thermal effects, where the consistency requirements are treated in a twofold sense. First, we propose a general constitutive formulation based on the foregoing separation as well as the two consistency criteria. This is accomplished by employing the corotational logarithmic rate and by incorporating an exactly integrable Eulerian rate equation for De for thermo-elastic behaviour. Then, we study the consistency of the formulation with thermodynamic laws. Towards this goal, simple forms of restrictions are derived, and consequences are discussed. It is shown that the proposed Eulerian formulation is free in the sense of thermodynamic consistency. Namely, a Helmholtz free energy function in explicit form may be found such that the restrictions from the thermodynamic laws can be fulfilled with positive internal dissipation for arbitrary forms of constitutive functions included in the constitutive formulation. In particular, that is the case for the foregoing essential constitutive structure in the purely mechanical case. These results eventually lead to a complete, explicit constitutive theory for coupled fields of deformation, stress and temperature in thermo

  7. The "Sadly Cannot" Thermodynamic Cycle Revisited.

    ERIC Educational Resources Information Center

    Mills, David S.; Huston, Craig S.

    1991-01-01

    An exercise that gives students a chance to use the equations of state for both an ideal gas and for an adiabatic process in determining the points at which heat flow reverses direction and at which the working substance reaches its maximum temperature is demonstrated. (KR)

  8. Summarizing lecture: factors influencing enzymatic H-transfers, analysis of nuclear tunnelling isotope effects and thermodynamic versus specific effects.

    PubMed

    Marcus, R A

    2006-08-29

    In the articles in this Discussion, a wide variety of topics are treated, including reorganization energy, initially introduced for electron transfers ('environmentally assisted tunnelling'), nuclear tunnelling, H/D and 12C/13C kinetic isotope effects (KIEs), the effect of changes of distal and nearby amino acid residues using site-directed mutagenesis, and dynamics versus statistical effects. A coordinate-free form of semi-classical theory is used to examine topics on data such as tunnelling versus 'over-the-barrier' paths and temperature and pressure effects on KIEs. The multidimensional semi-classical theory includes classically allowed and classically forbidden transitions. More generally, we address the question of relating kinetic to thermodynamic factors, as in the electron transfer field, so learning about specific versus thermodynamic effects in enzyme catalysis and KIEs.

  9. Summarizing lecture: factors influencing enzymatic H-transfers, analysis of nuclear tunnelling isotope effects and thermodynamic versus specific effects

    PubMed Central

    Marcus, R.A

    2006-01-01

    In the articles in this Discussion, a wide variety of topics are treated, including reorganization energy, initially introduced for electron transfers (‘environmentally assisted tunnelling’), nuclear tunnelling, H/D and C12/C13 kinetic isotope effects (KIEs), the effect of changes of distal and nearby amino acid residues using site-directed mutagenesis, and dynamics versus statistical effects. A coordinate-free form of semi-classical theory is used to examine topics on data such as tunnelling versus ‘over-the-barrier’ paths and temperature and pressure effects on KIEs. The multidimensional semi-classical theory includes classically allowed and classically forbidden transitions. More generally, we address the question of relating kinetic to thermodynamic factors, as in the electron transfer field, so learning about specific versus thermodynamic effects in enzyme catalysis and KIEs. PMID:16873131

  10. Gas dynamics of heat-release-induced waves in supercritical fluids: revisiting the Piston Effect

    NASA Astrophysics Data System (ADS)

    Migliorino, Mario Tindaro; Scalo, Carlo

    2016-11-01

    We investigate a gasdynamic approach to the modeling of heat-release-induced compression waves in supercritical fluids. We rely on highly resolved one-dimensional fully compressible Navier-Stokes simulations of CO2 at pseudo-boiling conditions in a closed duct inspired by the experiments of Miura et al.. Near-critical fluids exhibit anomalous variations of thermodynamic variables taken into account by adopting the Peng-Robinson equation of state and Chung's Method. An idealized heat source is applied, away from the boundaries, resulting in the generation of compression waves followed by contact discontinuities bounding a region of hot expanding fluid. For higher heat-release rates such compressions are coalescent with distinct shock-like features (i.e. non-isentropicity and propagation Mach numbers measurably greater than unity) and a non-uniform post-shock state, not present in ideal gas simulations, caused by the highly nonlinear equation of state. Thermoacoustic effects are limited to: (1) a one-way/one-time thermal-to-acoustic energy conversion, and (2) cumulative non-isentropic bulk heating due to the resonating compression waves, resulting in what is commonly referred to as the Piston Effect.

  11. Effect of hydrolysis on heat capacity, thermodynamic functions, and the relaxation transition of crab chitin and chitosan

    NASA Astrophysics Data System (ADS)

    Kashtanov, E. A.; Uryash, V. F.; Kokurina, N. Yu.; Larina, V. N.

    2014-02-01

    The heat capacity of crab chitin and chitosan is measured in a vacuum adiabatic calorimeter at 10-330 K. The thermodynamic characteristics (enthalpy, entropy, and Gibbs function) are calculated at T → 0 K to 330 K. Differential thermal analysis is used to calculate the relaxation transitions and thermal degradation of chitin and chitosan at 80-600 K. Acid hydrolysis is performed and its effect on the physicochemical properties and thermodynamic functions of chitin and chitosan is studied.

  12. Descriptive thermodynamics

    NASA Astrophysics Data System (ADS)

    Ford, David; Huntsman, Steven

    2006-06-01

    Thermodynamics (in concert with its sister discipline, statistical physics) can be regarded as a data reduction scheme based on partitioning a total system into a subsystem and a bath that weakly interact with each other. Whereas conventionally, the systems investigated require this form of data reduction in order to facilitate prediction, a different problem also occurs, in the context of communication networks, markets, etc. Such “empirically accessible” systems typically overwhelm observers with the sort of information that in the case of (say) a gas is effectively unobtainable. What is required for such complex interacting systems is not prediction (this may be impossible when humans besides the observer are responsible for the interactions) but rather, description as a route to understanding. Still, the need for a thermodynamical data reduction scheme remains. In this paper, we show how an empirical temperature can be computed for finite, empirically accessible systems, and further outline how this construction allows the age-old science of thermodynamics to be fruitfully applied to them.

  13. Statistical thermodynamics of aerosols and the gas-solid Joule-Thomson effect

    NASA Astrophysics Data System (ADS)

    Pierotti, Robert A.; Rybolt, Thomas R.

    1984-04-01

    Due to the adsorption of a gas by a solid, it is expected that an aerosol created by dispersing a fine powder in a gas would have unique thermodynamic properties not found in pure or mixed gases. The virial equation of state associated with an aerosol dusty gas is obtained from statistical thermodynamic considerations. In the theoretical model presented here, the aerosol is considered to be a two component fluid made up of solid particles and gas molecules. The aerosol virial equation of state is used to derive an expression for the Joule-Thomson effect associated with a gas-solid dispersion. The magnitude of the gas-solid Joule-Thomson effect is expressed in terms of gas and gas-solid virial coefficients. Previous adsorption data for an argon-porous carbon system is used to obtain gas-solid virial coefficients and to predict the magnitude of the gas-solid Joule-Thomson effect. A significant enhancement of the Joule-Thomson effect is predicted for gas-solid systems which display a strong interaction. For example, at a temperature of 300 K an argon-Saran 746 porous carbon aerosol system at a concentration of (0.4 g of powder/l of gas) is predicted to have a gas-solid Joule-Thomson coefficient of 3.6 K/atm which is ten times greater than the effect for pure argon.

  14. Aerosol effect on the evolution of the thermodynamic properties of warm convective cloud fields

    PubMed Central

    Dagan, Guy; Koren, Ilan; Altaratz, Orit; Heiblum, Reuven H.

    2016-01-01

    Convective cloud formation and evolution strongly depend on environmental temperature and humidity profiles. The forming clouds change the profiles that created them by redistributing heat and moisture. Here we show that the evolution of the field’s thermodynamic properties depends heavily on the concentration of aerosol, liquid or solid particles suspended in the atmosphere. Under polluted conditions, rain formation is suppressed and the non-precipitating clouds act to warm the lower part of the cloudy layer (where there is net condensation) and cool and moisten the upper part of the cloudy layer (where there is net evaporation), thereby destabilizing the layer. Under clean conditions, precipitation causes net warming of the cloudy layer and net cooling of the sub-cloud layer (driven by rain evaporation), which together act to stabilize the atmosphere with time. Previous studies have examined different aspects of the effects of clouds on their environment. Here, we offer a complete analysis of the cloudy atmosphere, spanning the aerosol effect from instability-consumption to enhancement, below, inside and above warm clouds, showing the temporal evolution of the effects. We propose a direct measure for the magnitude and sign of the aerosol effect on thermodynamic instability. PMID:27929097

  15. Aerosol effect on the evolution of the thermodynamic properties of warm convective cloud fields

    NASA Astrophysics Data System (ADS)

    Dagan, Guy; Koren, Ilan; Altaratz, Orit; Heiblum, Reuven H.

    2016-12-01

    Convective cloud formation and evolution strongly depend on environmental temperature and humidity profiles. The forming clouds change the profiles that created them by redistributing heat and moisture. Here we show that the evolution of the field’s thermodynamic properties depends heavily on the concentration of aerosol, liquid or solid particles suspended in the atmosphere. Under polluted conditions, rain formation is suppressed and the non-precipitating clouds act to warm the lower part of the cloudy layer (where there is net condensation) and cool and moisten the upper part of the cloudy layer (where there is net evaporation), thereby destabilizing the layer. Under clean conditions, precipitation causes net warming of the cloudy layer and net cooling of the sub-cloud layer (driven by rain evaporation), which together act to stabilize the atmosphere with time. Previous studies have examined different aspects of the effects of clouds on their environment. Here, we offer a complete analysis of the cloudy atmosphere, spanning the aerosol effect from instability-consumption to enhancement, below, inside and above warm clouds, showing the temporal evolution of the effects. We propose a direct measure for the magnitude and sign of the aerosol effect on thermodynamic instability.

  16. Aerosol effect on the evolution of the thermodynamic properties of warm convective cloud fields.

    PubMed

    Dagan, Guy; Koren, Ilan; Altaratz, Orit; Heiblum, Reuven H

    2016-12-08

    Convective cloud formation and evolution strongly depend on environmental temperature and humidity profiles. The forming clouds change the profiles that created them by redistributing heat and moisture. Here we show that the evolution of the field's thermodynamic properties depends heavily on the concentration of aerosol, liquid or solid particles suspended in the atmosphere. Under polluted conditions, rain formation is suppressed and the non-precipitating clouds act to warm the lower part of the cloudy layer (where there is net condensation) and cool and moisten the upper part of the cloudy layer (where there is net evaporation), thereby destabilizing the layer. Under clean conditions, precipitation causes net warming of the cloudy layer and net cooling of the sub-cloud layer (driven by rain evaporation), which together act to stabilize the atmosphere with time. Previous studies have examined different aspects of the effects of clouds on their environment. Here, we offer a complete analysis of the cloudy atmosphere, spanning the aerosol effect from instability-consumption to enhancement, below, inside and above warm clouds, showing the temporal evolution of the effects. We propose a direct measure for the magnitude and sign of the aerosol effect on thermodynamic instability.

  17. Effects of a scalar field on the thermodynamics of interuniversal entanglement

    NASA Astrophysics Data System (ADS)

    Garay, Iñaki; Robles-Pérez, Salvador

    2014-03-01

    We consider a multiverse scenario made up of classically disconnected regions of the spacetime that are, nevertheless, in a quantum entangled state. The addition of a scalar field enriches the model and allows us to treat both the inflationary and the "oscillatory stage" of the universe on the same basis. Imposing suitable boundary conditions on the state of the multiverse, two different representations are constructed related by a Bogoliubov transformation. We compute the thermodynamic magnitudes of the entanglement, such as entropy and energy, explore the effects introduced by the presence of the scalar field and compare with previous results in the absence of scalar field.

  18. Effect of drop size on the impact thermodynamics for supercooled large droplet in aircraft icing

    NASA Astrophysics Data System (ADS)

    Zhang, Chen; Liu, Hong

    2016-06-01

    Supercooled large droplet (SLD), which can cause abnormal icing, is a well-known issue in aerospace engineering. Although efforts have been exerted to understand large droplet impact dynamics and the supercooled feature in the film/substrate interface, respectively, the thermodynamic effect during the SLD impact process has not received sufficient attention. This work conducts experimental studies to determine the effects of drop size on the thermodynamics for supercooled large droplet impingement. Through phenomenological reproduction, the rapid-freezing characteristics are observed in diameters of 400, 800, and 1300 μm. The experimental analysis provides information on the maximum spreading rate and the shrinkage rate of the drop, the supercooled diffusive rate, and the freezing time. A physical explanation of this unsteady heat transfer process is proposed theoretically, which indicates that the drop size is a critical factor influencing the supercooled heat exchange and effective heat transfer duration between the film/substrate interface. On the basis of the present experimental data and theoretical analysis, an impinging heating model is developed and applied to typical SLD cases. The model behaves as anticipated, which underlines the wide applicability to SLD icing problems in related fields.

  19. Many-Body Effects on the Thermodynamics of Fluids, Mixtures, and Nanoconfined Fluids.

    PubMed

    Desgranges, Caroline; Delhommelle, Jerome

    2015-11-10

    Using expanded Wang-Landau simulations, we show that taking into account the many-body interactions results in sharp changes in the grand-canonical partition functions of single-component systems, binary mixtures, and nanoconfined fluids. The many-body contribution, modeled with a 3-body Axilrod-Teller-Muto term, results in shifts toward higher chemical potentials of the phase transitions from low-density phases to high-density phases and accounts for deviations of more than, e.g., 20% of the value of the partition function for a single-component liquid. Using the statistical mechanics formalism, we analyze how this contribution has a strong impact on some properties (e.g., pressure, coexisting densities, and enthalpy) and a moderate impact on others (e.g., Gibbs or Helmholtz free energies). We also characterize the effect of the 3-body terms on adsorption isotherms and adsorption thermodynamic properties, thereby providing a full picture of the effect of the 3-body contribution on the thermodynamics of nanoconfined fluids.

  20. Differential Effects of Hydrophobic Core Packing Residues for Thermodynamic and Mechanical Stability of a Hyperthermophilic Protein.

    PubMed

    Tych, Katarzyna M; Batchelor, Matthew; Hoffmann, Toni; Wilson, Michael C; Hughes, Megan L; Paci, Emanuele; Brockwell, David J; Dougan, Lorna

    2016-07-26

    Proteins from organisms that have adapted to environmental extremes provide attractive systems to explore and determine the origins of protein stability. Improved hydrophobic core packing and decreased loop-length flexibility can increase the thermodynamic stability of proteins from hyperthermophilic organisms. However, their impact on protein mechanical stability is not known. Here, we use protein engineering, biophysical characterization, single-molecule force spectroscopy (SMFS), and molecular dynamics (MD) simulations to measure the effect of altering hydrophobic core packing on the stability of the cold shock protein TmCSP from the hyperthermophilic bacterium Thermotoga maritima. We make two variants of TmCSP in which a mutation is made to reduce the size of aliphatic groups from buried hydrophobic side chains. In the first, a mutation is introduced in a long loop (TmCSP L40A); in the other, the mutation is introduced on the C-terminal β-strand (TmCSP V62A). We use MD simulations to confirm that the mutant TmCSP L40A shows the most significant increase in loop flexibility, and mutant TmCSP V62A shows greater disruption to the core packing. We measure the thermodynamic stability (ΔGD-N) of the mutated proteins and show that there is a more significant reduction for TmCSP L40A (ΔΔG = 63%) than TmCSP V62A (ΔΔG = 47%), as might be expected on the basis of the relative reduction in the size of the side chain. By contrast, SMFS measures the mechanical stability (ΔG*) and shows a greater reduction for TmCSP V62A (ΔΔG* = 8.4%) than TmCSP L40A (ΔΔG* = 2.5%). While the impact on the mechanical stability is subtle, the results demonstrate the power of tuning noncovalent interactions to modulate both the thermodynamic and mechanical stability of a protein. Such understanding and control provide the opportunity to design proteins with optimized thermodynamic and mechanical properties.

  1. Thermodynamic Study on Plasma Expansion along a Divergent Magnetic Field.

    PubMed

    Zhang, Yunchao; Charles, Christine; Boswell, Rod

    2016-01-15

    Thermodynamic properties are revisited for electrons that are governed by nonlocal electron energy probability functions in a plasma of low collisionality. Measurements in a laboratory helicon double layer experiment have shown that the effective electron temperature and density show a polytropic correlation with an index of γ_{e}=1.17±0.02 along the divergent magnetic field, implying a nearly isothermal plasma (γ_{e}=1) with heat being brought into the system. However, the evolution of electrons along the divergent magnetic field is essentially an adiabatic process, which should have a γ_{e}=5/3. The reason for this apparent contradiction is that the nearly collisionless plasma is very far from local thermodynamic equilibrium and the electrons behave nonlocally. The corresponding effective electron enthalpy has a conservation relation with the potential energy, which verifies that there is no heat transferred into the system during the electron evolution. The electrons are shown in nonlocal momentum equilibrium under the electric field and the gradient of the effective electron pressure. The convective momentum of ions, which can be assumed as a cold species, is determined by the effective electron pressure and the effective electron enthalpy is shown to be the source for ion acceleration. For these nearly collisionless plasmas, the use of traditional thermodynamic concepts can lead to very erroneous conclusions regarding the thermal conductivity.

  2. Non-locality, adiabaticity, thermodynamics and electron energy probability functions

    NASA Astrophysics Data System (ADS)

    Boswell, Roderick; Zhang, Yunchao; Charles, Christine; Takahashi, Kazunori

    2016-09-01

    Thermodynamic properties are revisited for electrons that are governed by nonlocal electron energy probability functions in a plasma of low collisionality. Measurements in a laboratory helicon double layer experiment have shown that the effective electron temperature and density show a polytropic correlation with an index of γe = 1 . 17 +/- 0 . 02 along the divergent magnetic field, implying a nearly isothermal plasma (γe = 1) with heat being brought into the system. However, the evolution of electrons along the divergent magnetic field is essentially an adiabatic process, which should have a γe = 5 / 3 . The reason for this apparent contradiction is that the nearly collisionless plasma is very far from local thermodynamic equilibrium and the electrons behave nonlocally. The corresponding effective electron enthalpy has a conservation relation with the potential energy, which verifies that there is no heat transferred into the system during the electron evolution. The electrons are shown in nonlocal momentum equilibrium under the electric field and the gradient of the effective electron pressure. The convective momentum of ions, which can be assumed as a cold species, is determined by the effective electron pressure and the effective electron enthalpy is shown to be the source for ion acceleration. For these nearly collisionless plasmas, the use of traditional thermodynamic concepts can lead to very erroneous conclusions regarding the thermal conductivity.

  3. Analysis of water sorption isotherms of amorphous food materials by solution thermodynamics with relevance to glass transition: evaluation of plasticizing effect of water by the thermodynamic parameters.

    PubMed

    Shimazaki, Eriko; Tashiro, Akiko; Kumagai, Hitomi; Kumagai, Hitoshi

    2017-04-01

    Relation between the thermodynamic parameters obtained from water sorption isotherms and the degree of reduction in the glass transition temperature (Tg), accompanied by water sorption, was quantitatively studied. Two well-known glassy food materials namely, wheat gluten and maltodextrin were used as samples. The difference between the chemical potential of water in a solution and that of pure water ([Formula: see text]), the difference between the chemical potential of solid in a solution and that of a pure solid ([Formula: see text]), and the change in the integral Gibbs free energy ([Formula: see text]) were obtained by analyzing the water sorption isotherms using solution thermodynamics. The parameter [Formula: see text] correlated well with ΔTg (≡Tg - Tg0; where Tg0 is the glass transition temperature of dry material), which had been taken to be an index of plasticizing effect. This indicates that plasticizing effect of water on foods can be evaluated through the parameter [Formula: see text].

  4. The effect of thermodynamic data on computer model predictions of uranium speciation in natural water systems.

    PubMed

    Unsworth, Emily R; Jones, Phil; Hill, Steve J

    2002-08-01

    Computer models have found widespread application in order to help elucidate and predict changes in environmental systems. One such application is the prediction of trace metal speciation in aqueous systems. This is achieved by solving a set of non-linear equations involving equilibrium constants for all the components in the system, within mass and charge balance constraints. In this study a comparison of the predicted uranium speciation from two computer programs, WHAM and PHREEQCI, is used to illustrate the effect variations in thermodynamic data can have on the models produced. Using the original thermodynamic data provided with the models, WHAM predicted the UO2(2+) ion as the major species (84%) while PHREEQCI predicted UO2(HPO4)2(2-) as the major species (86%). Substituting uranium data from the Nuclear Energy Agency Thermochemical Database project (NEA-TDB) into both programs produced similar results from each program, with UO2F+ predicted to dominate (68%) in a groundwater sample. Natural water samples often contain humic substances. The possible interaction of such substances with uranium was also modelled. The WHAM program includes a discreet site electrostatic humic substance model, however in order to use the PHREEQCI program to model humic substance interactions, a 'model fulvic acid' dataset was added to the program. These models predicted 85 to 98% uranium-humic substance species at neutral pH. This indicates that humic substances do need to be taken into account when modelling uranium speciation in natural water samples.

  5. Effective rates from thermodynamically consistent coarse-graining of models for molecular motors with probe particles.

    PubMed

    Zimmermann, Eva; Seifert, Udo

    2015-02-01

    Many single-molecule experiments for molecular motors comprise not only the motor but also large probe particles coupled to it. The theoretical analysis of these assays, however, often takes into account only the degrees of freedom representing the motor. We present a coarse-graining method that maps a model comprising two coupled degrees of freedom which represent motor and probe particle to such an effective one-particle model by eliminating the dynamics of the probe particle in a thermodynamically and dynamically consistent way. The coarse-grained rates obey a local detailed balance condition and reproduce the net currents. Moreover, the average entropy production as well as the thermodynamic efficiency is invariant under this coarse-graining procedure. Our analysis reveals that only by assuming unrealistically fast probe particles, the coarse-grained transition rates coincide with the transition rates of the traditionally used one-particle motor models. Additionally, we find that for multicyclic motors the stall force can depend on the probe size. We apply this coarse-graining method to specific case studies of the F(1)-ATPase and the kinesin motor.

  6. Effect of thermodynamic activity on skin permeation and skin concentration of triamcinolone acetonide.

    PubMed

    Ishii, Hiroshi; Todo, Hiroaki; Sugibayashi, Kenji

    2010-04-01

    Effects of thermodynamic activity and the state (solution/suspension) of triamcinolone acetonide (TA) on skin permeation and concentration were physicochemically and kinetically analyzed. Permeation of TA through a silicone membrane, hairless rat skin (full-thickness skin or stripped skin) or a three-dimensional cultured human skin model (LSE-high) was determined and a permeability coefficient (P), partition coefficient (K) , diffusion coefficient (D) and steady-state flux (J) were calculated. The resulting J values proportionally increased with an increase in the TA activity in the drug solution and similar P, K and D values were obtained independent of the TA state (solution/suspension) in all membranes except for full-thickness hairless rat skin. On the other hand, the TA permeation through full-thickness hairless rat skin with the 1000 microg/ml suspension was higher than that expected judging by the thermodynamic acidity of TA. Higher D and P values were also obtained in the skin permeation of TA from the 1000 microg/ml suspension. Morphological observation of the skin surface by scanning electron microscope (SEM) showed the presence of TA solids in the hair follicles after application of the TA suspension. These results suggest that dissolved TA may be permeated predominantly through the stratum corneum, but that solid TA may be passed through the hair follicles to enter the dermis. The present physicochemical and kinetic analysis provides useful information to develop topical steroid formulations.

  7. Testing the Effects of Helium Pressurant on Thermodynamic Vent System Performance with Liquid Hydrogen

    NASA Astrophysics Data System (ADS)

    Flachbart, R. H.; Hastings, L. J.; Hedayat, A.; Nelson, S. L.; Tucker, S.

    2008-03-01

    In support of the development of a micro-gravity pressure control capability for liquid hydrogen, testing was conducted at the Marshall Space Flight Center (MSFC) with the Multipurpose Hydrogen Test Bed (MHTB) to evaluate the effects of helium pressurant on the performance of a spray-bar thermodynamic vent system (TVS). The testing, with an ambient heat leak of about 70 W and tank fill levels of 90, 50, and 25%, was performed for 14 days during August and September 2005. The TVS successfully controlled the tank pressure within a ±3.45 kPa band with various gaseous helium (GHe) masses in the ullage. Relative to pressure control with an "all hydrogen" ullage, the GHe presence resulted in 37 to 68% longer pressure reduction cycle durations, depending on the fill level, during the mixing/venting phase of the control cycle. Testing was also conducted to evaluate thermodynamic venting without the recirculation pump operating, at a very low fill level. Although ullage stratification was present, the ullage pressure was successfully controlled without the pump. It was evident that the spray-bar and heat exchanger configuration, which extended almost the entire length of the tank, enabled significant thermal energy removal from the ullage even without the pump operating.

  8. Thermodynamic analysis and experimental study of the effect of atmospheric pressure on the ice point

    NASA Astrophysics Data System (ADS)

    Harvey, A. H.; McLinden, M. O.; Tew, W. L.

    2013-09-01

    We present a detailed thermodynamic analysis of the temperature of the ice point as a function of atmospheric pressure. This analysis makes use of accurate international standards for the properties of water and ice, and of available high-accuracy data for the Henry's constants of atmospheric gases in liquid water. The result is an ice point of 273.150 019(5) K at standard atmospheric pressure, with higher ice-point temperatures (varying nearly linearly with pressure) at lower pressures. The effect of varying ambient CO2 concentration is analyzed and found to be significant in comparison to other uncertainties in the model. The thermodynamic analysis is compared with experimental measurements of the temperature difference between the ice point and the triple point of water performed at elevations ranging from 145 m to 4302 m, with atmospheric pressures from 101 kPa to 60 kPa. At the request of the authors and the Proceedings Editor the above article has been replaced with a corrected version. The original PDF file supplied to AIP Publishing contained several equations with incorrect/missing characters resulting from processes used to create the PDF file. The article has been replaced and the equations now display correctly.

  9. Towards a probabilistic definition of entropy: An investigation of the effects of a new curriculum on students' understanding of thermodynamics

    NASA Astrophysics Data System (ADS)

    Colon-Garcia, Evy B.

    Thermodynamics is a vital tool in understanding why reactions happen; nevertheless, it is often considered a difficult topic. Prior studies have shown that students struggle with fundamental thermodynamic concepts such as entropy, enthalpy and Gibbs energy even in upper level physical chemistry courses. Thermodynamics, as a general chemistry topic, can be more math-intensive than other topics such as bonding or intermolecular forces. As a result, it is possible for students to get lost in the algorithms and overlook the important underlying theoretical concepts. Students' difficulties in understanding thermodynamics may be contributing to their inability to explain phenomena such as phase changes and manipulations of equilibrium systems. Current chemistry curricula split the thermodynamic chapters over a span of two semesters as well as splitting it over different units. This division fails to make explicit the connection between Enthalpy, Entropy and Gibbs Energy and how they affect how and why every reaction or process happens. The reason for this division of topics is not based on any educational research rather than opinions as to what will not overwhelm the students. Additionally, students who take only one semester of General Chemistry will leave without being instructed in what is considered to be one of the most fundamental concepts in Chemistry, Thermodynamics. Chemistry, Life, the Universe and Everything (CLUE) is a general chemistry course developed with the explicit goal of addressing the major obstacles that inhibit students from acquiring an appreciation and mastery of the chemical principles upon which other sciences depend. Using a control and treatment group, the effectiveness of this new curriculum was evaluated for two main aspects: 1. What is students' understanding of entropy?, 2. Can an alternative instructional approach to teaching Thermodynamics (Chemistry, Life, the Universe and Everything - CLUE) improve students' understanding of Entropy

  10. Confinement Effects on the Thermodynamics of Protein Folding: Monte Carlo Simulations

    PubMed Central

    Rathore, Nitin; Knotts, Thomas A.; de Pablo, Juan J.

    2006-01-01

    The effects of chaperonin-like cage-induced confinement on protein stability have been studied for molecules of varying sizes and topologies. Minimalist models based on Gō-like interactions are employed for the proteins, and density-of-states-based Monte Carlo simulations are performed to accurately characterize the thermodynamic transitions. This method permits efficient sampling of conformational space and yields precise estimates of free energy and entropic changes associated with protein folding. We find that confinement-driven stabilization is not only dependent on protein size and cage radius, but also on the specific topology. The choice of the confining potential is also shown to have an effect on the observed stabilization and the scaling behavior of the stabilization with respect to the cage size. PMID:16361344

  11. Confinement effects on the thermodynamics of protein folding: Monte Carlo simulations.

    PubMed

    Rathore, Nitin; Knotts, Thomas A; de Pablo, Juan J

    2006-03-01

    The effects of chaperonin-like cage-induced confinement on protein stability have been studied for molecules of varying sizes and topologies. Minimalist models based on Gō-like interactions are employed for the proteins, and density-of-states-based Monte Carlo simulations are performed to accurately characterize the thermodynamic transitions. This method permits efficient sampling of conformational space and yields precise estimates of free energy and entropic changes associated with protein folding. We find that confinement-driven stabilization is not only dependent on protein size and cage radius, but also on the specific topology. The choice of the confining potential is also shown to have an effect on the observed stabilization and the scaling behavior of the stabilization with respect to the cage size.

  12. Thermodynamic properties of non-conformal soft-sphere fluids with effective hard-sphere diameters.

    PubMed

    Rodríguez-López, Tonalli; del Río, Fernando

    2012-01-28

    In this work we study a set of soft-sphere systems characterised by a well-defined variation of their softness. These systems represent an extension of the repulsive Lennard-Jones potential widely used in statistical mechanics of fluids. This type of soft spheres is of interest because they represent quite accurately the effective intermolecular repulsion in fluid substances and also because they exhibit interesting properties. The thermodynamics of the soft-sphere fluids is obtained via an effective hard-sphere diameter approach that leads to a compact and accurate equation of state. The virial coefficients of soft spheres are shown to follow quite simple relationships that are incorporated into the equation of state. The approach followed exhibits the rescaling of the density that produces a unique equation for all systems and temperatures. The scaling is carried through to the level of the structure of the fluids.

  13. An effective pair potential for thermodynamics and structural properties of liquid mercury.

    PubMed

    Bomont, Jean-Marc; Bretonnet, Jean-Louis

    2006-02-07

    The properties of liquid mercury are investigated by using an empirical effective pair potential. Its parameters are determined with the aid of Monte Carlo simulation along the liquid branch of the liquid-vapor coexistence curve. The complexity of the electronic structure of dense metal mercury supposes a state dependence of the interatomic interactions, while no more state dependence is found in the metal-nonmetal transition region. It is shown that the use of this effective potential leads to an accurate description of the structural and thermodynamic properties of the expanded liquid mercury. Then, the melting and freezing phenomena are investigated with that potential. Sharp melting and freezing temperatures are observed at 234 and 169 K, respectively. This large hysteresis loop between freezing and melting is consistent with the experiments for the bulk mercury.

  14. Thermodynamic constraints on effective energy and mass transfer and catchment function

    NASA Astrophysics Data System (ADS)

    Rasmussen, C.

    2012-03-01

    Understanding how water, energy and carbon are partitioned to primary production and effective precipitation is central to quantifying the limits on critical zone evolution. Recent work suggests quantifying energetic transfers to the critical zone in the form of effective precipitation and primary production provides a first order approximation of critical zone process and structural organization. However, explicit linkage of this effective energy and mass transfer (EEMT; W m-2) to critical zone state variables and well defined physical limits remains to be developed. The objective of this work was to place EEMT in the context of thermodynamic state variables of temperature and vapor pressure deficit, with explicit definition of EEMT physical limits using a global climate dataset. The relation of EEMT to empirical measures of catchment function was also examined using a subset of the Model Parameter Estimation Experiment (MOPEX) catchments. The data demonstrated three physical limits for EEMT: (i) an absolute vapor pressure deficit threshold of 1200 Pa above which EEMT is zero; (ii) a temperature dependent vapor pressure deficit limit following the saturated vapor pressure function up to a temperature of 292 K; and (iii) a minimum precipitation threshold required from EEMT production at temperatures greater than 292 K. Within these limits, EEMT scales directly with precipitation, with increasing conversion of the precipitation to EEMT with increasing temperature. The state-space framework derived here presents a simplified framework with well-defined physical limits that has the potential for directly integrating regional to pedon scale heterogeneity in effective energy and mass transfer relative to critical zone structure and function within a common thermodynamic framework.

  15. Thermodynamic constraints on effective energy and mass transfer and catchment function

    NASA Astrophysics Data System (ADS)

    Rasmussen, C.

    2011-07-01

    Understanding how water, energy and carbon are partitioned to primary production and effective precipitation is central to quantifying the limits on critical zone evolution. Recent work suggests quantifying energetic transfers to the critical zone in the form of effective precipitation and primary production provides a first order approximation of critical zone process and structural organization. However, explicit linkage of this effective energy and mass transfer (EEMT; W m-2) to critical zone state variables and well defined physical limits remains to be developed. The objective of this work was to place EEMT in the context of thermodynamic state variables of temperature and vapor pressure deficit, with explicit definition of EEMT physical limits using a global climate dataset. The relation of EEMT to empirical measures of catchment function was also examined using a subset of the Model Parameter Estimation Experiment (MOPEX) catchments. The data demonstrated three physical limits for EEMT: (i) an absolute vapor pressure deficit threshold of 1200 Pa above which EEMT is zero; (ii) a temperature dependent vapor pressure deficit limit following the saturated vapor pressure function up to a temperature of 292 K; and (iii) a minimum precipitation threshold required from EEMT production at temperatures greater than 292 K. Within these limits, EEMT scales directly with precipitation, with increasing conversion of the precipitation to EEMT with increasing temperature. The state-space framework derived here presents a simplified framework with well-defined physical limits that has the potential for directly integrating regional to pedon scale heterogeneity in effective energy and mass transfer relative to critical zone structure and function within a common thermodynamic framework.

  16. Effect of drying methods on the moisture sorption isotherms and thermodynamic properties of mint leaves.

    PubMed

    Dalgıç, Ali Coşkun; Pekmez, Hatice; Belibağlı, Kadir Bülent

    2012-08-01

    Mint leaves were dried by three different types of dryers, namely; tray, freeze and distributed (indirect)-type solar dryer. Sorption isotherms of fresh, solar, tray and freeze dried mint were determined at temperatures of 15 °C, 25 °C and 35 °C over a range of relative humidities (10-90%). The effect of drying method on the water sorption isotherms of dried mint samples was evaluated. Experimental data were used to determine the best models for predicting the moisture sorption content of mint. Among nine sorption models tested, Peleg, GAB, Lewicki and modified Mizrahi equations gave the best fit to experimental data. The sorption data were analyzed for determination of monolayer moisture content, density of sorbed water, number of adsorbed monolayers, percent bound water, and surface area of adsorbance. The experimental data were also used to determine some thermodynamic properties of mint.

  17. Tabulation and summary of thermodynamic effects data for developed cavitation on ogive-nosed bodies

    NASA Technical Reports Server (NTRS)

    Holl, J. W.; Billet, M. L.; Weir, D. S.

    1978-01-01

    Thermodynamic effects data for developed cavitation on zero and quarter caliber ogives in Freon 113 and water are tabulated and summarized. These data include temperature depression (delta T), flow coefficient (C sub Q), and various geometrical characteristics of the cavity. For the delta T tests, the free-stream temperature varied from 35 C to 95 C in Freon 113 and from 60 C to 125 C in water for a velocity range of 19.5 m/sec to 36.6 m/sec. Two correlations of the delta T data by the entrainment method are presented. These correlations involve different combinations of the Nusselt, Reynolds, Froude, Weber, and Peclet numbers and dimensionless cavity length.

  18. Thermodynamic and kinetic stability of zwitterionic histidine: Effects of gas phase hydration

    NASA Astrophysics Data System (ADS)

    Lee, Sung-Sik; Kim, Ju-Young; Han, Yuna; Shim, Hyun-Jin; Lee, Sungyul

    2015-09-01

    We present calculations for histidine-(H2O)n (n = 0-6) to examine the effects of micro-hydrating water molecules on the relative stability of the zwitterionic vs. canonical forms of histidine. We calculate the structures and Gibbs free energies of the conformers at wB97XD/6-311++G(d,p) level of theory. We find that six water molecules are required to produce the thermodynamically stable histidine zwitterion. By calculating the barriers of canonical ↔ zwitterionic transformation, we predict that both the most stable canonical and zwitterionic forms of histidine-(H2O)6 may be observed in low temperature gas phase environment.

  19. Experimental determination of the thermodynamic parameters affecting the adsorption behaviour and dispersion effectiveness of PCE superplasticizers

    SciTech Connect

    Plank, J.; Sachsenhauser, B.; Reese, J. de

    2010-05-15

    For adsorption of three different allylether-based PCE superplasticizers on CaCO{sub 3} surface, the thermodynamic parameters DELTAH, DELTAS and DELTAG were determined experimentally. The GIBBS standard free energy of adsorption DELTAG{sub 0ads}, the standard enthalpy of adsorption DELTAH{sub 0ads} and the standard entropy of adsorption DELTAS{sub 0ads} applying to an unoccupied CaCO{sub 3} surface were obtained via a linear regression of ln K (equilibrium constant) versus 1 / T (VAN'T HOFF plot). Additionally, the thermodynamic parameters characteristic for a CaCO{sub 3} surface loaded already with polymer (isosteric conditions) were determined using a modified CLAUSIUS-CLAPEYRON equation. For all PCE molecules, negative DELTAG values were found, indicating that adsorption of these polymers is energetically favourable and a spontaneous process. Adsorption of PCEs possessing short side chains is mainly instigated by electrostatic attraction and a release of enthalpy. Contrary to this, adsorption of PCEs with long side chains occurs because of a huge gain in entropy. The gain in entropy results from the release of counter ions attached to the carboxylate groups of the polymer backbone and of water molecules and ions adsorbed on the CaCO{sub 3} surface. With increased surface loading, however, DELTAG{sub isosteric} decreases and adsorption ceases when DELTAG becomes 0. The presence of Ca{sup 2+} ions in the pore solution strongly impacts PCE adsorption, due to complexation of carboxylate groups and a reduced anionic charge amount of the molecule. In the presence of Ca{sup 2+}, adsorption of allylether-based PCEs is almost exclusively driven by a gain in entropy. Consequently, PCEs should produce a strong entropic effect upon adsorption to be effective cement dispersants. Molecular architecture, anionic charge density and molecular weight as well as the type of anchor groups present in a superplasticizer determine whether enthalpy or entropy is the dominant force for

  20. The effect of substrate on thermodynamic and kinetic anisotropies in atomic thin films

    SciTech Connect

    Haji-Akbari, Amir; Debenedetti, Pablo G.

    2014-07-14

    Glasses have a wide range of technological applications. The recent discovery of ultrastable glasses that are obtained by depositing the vapor of a glass-forming liquid onto the surface of a cold substrate has sparked renewed interest in the effects of confinements on physicochemical properties of liquids and glasses. Here, we use molecular dynamics simulations to study the effect of substrate on thin films of a model glass-forming liquid, the Kob-Andersen binary Lennard-Jones system, and compute profiles of several thermodynamic and kinetic properties across the film. We observe that the substrate can induce large oscillations in profiles of thermodynamic properties such as density, composition, and stress, and we establish a correlation between the oscillations in total density and the oscillations in normal stress. We also demonstrate that the kinetic properties of an atomic film can be readily tuned by changing the strength of interactions between the substrate and the liquid. Most notably, we show that a weakly attractive substrate can induce the emergence of a highly mobile region in its vicinity. In this highly mobile region, structural relaxation is several times faster than in the bulk, and the exploration of the potential energy landscape is also more efficient. In the subsurface region near a strongly attractive substrate, however, the dynamics is decelerated and the sampling of the potential energy landscape becomes less efficient than the bulk. We explain these two distinct behaviors by establishing a correlation between the oscillations in kinetic properties and the oscillations in lateral stress. Our findings offer interesting opportunities for designing better substrates for the vapor deposition process or developing alternative procedures for situations where vapor deposition is not feasible.

  1. Thermodynamic theory of strain-mediated direct magnetoelectric effect in multiferroic film-substrate hybrids.

    PubMed

    Kukhar, V G; Pertsev, N A; Kholkin, A L

    2010-07-02

    A nonlinear thermodynamic theory is developed for the strain-mediated direct magnetoelectric (ME) effect displayed by ferroelectric-ferromagnetic nanostructures. This effect results from transmission of magnetic-field-induced deformations of a thick ferromagnetic substrate to a thin ferroelectric overlayer, where the polarization changes due to lattice strains. The strain-dependent polarization and permittivity of an epitaxial nanolayer (few tens of nm thick) are calculated using the thermodynamic theory of single-domain ferroelectric films. The substrate magnetostrictive deformations are described phenomenologically, taking into account their nonlinear variation with magnetic field. The calculations show that ME polarization and voltage coefficients strongly depend on the initial strain state of the film. For BaTiO(3) and PbTiO(3) films deposited on Co(0.8)Zn(0.2)Fe(2)O(4), the out-of-plane polarization and related ME coefficients are calculated numerically as a function of magnetic field parallel to the interface. For films stabilized in the monoclinic phase, this transverse ME response depends on the orientation of magnetic field relative to their in-plane crystallographic axes. The longitudinal ME coefficient is also evaluated and, for a substrate geometry minimizing the demagnetizing field, predicted to be comparable to the transverse one. For BaTiO(3) and PbTiO(3) films deposited on Terfenol-D, the calculations yield high ME polarization coefficients approximately 10(-7) s m(-1) and giant ME voltage coefficients approximately 50 V cm(-1) Oe(-1).

  2. REVISITING THE FIRST GALAXIES: THE EFFECTS OF POPULATION III STARS ON THEIR HOST GALAXIES

    SciTech Connect

    Muratov, Alexander L.; Gnedin, Oleg Y.; Zemp, Marcel; Gnedin, Nickolay Y.

    2013-08-01

    We revisit the formation and evolution of the first galaxies using new hydrodynamic cosmological simulations with the adaptive refinement tree code. Our simulations feature a recently developed model for H{sub 2} formation and dissociation, and a star formation recipe that is based on molecular rather than atomic gas. Here, we develop and implement a recipe for the formation of metal-free Population III (Pop III) stars in galaxy-scale simulations that resolve primordial clouds with sufficiently high density. We base our recipe on the results of prior zoom-in simulations that resolved the protostellar collapse in pre-galactic objects. We find the epoch during which Pop III stars dominated the energy and metal budget of the first galaxies to be short-lived. Galaxies that host Pop III stars do not retain dynamical signatures of their thermal and radiative feedback for more than 10{sup 8} years after the lives of the stars end in pair-instability supernovae, even when we consider the maximum reasonable efficiency of the feedback. Though metals ejected by the supernovae can travel well beyond the virial radius of the host galaxy, they typically begin to fall back quickly, and do not enrich a large fraction of the intergalactic medium. Galaxies with a total mass in excess of 3 Multiplication-Sign 10{sup 6} M{sub Sun} re-accrete most of their baryons and transition to metal-enriched Pop II star formation.

  3. Thermodynamic Effect of Platinum Addition to beta-NiAl: An Initial Investigation

    NASA Technical Reports Server (NTRS)

    2005-01-01

    An initial investigation was conducted to determine the effect of platinum addition on the activities of aluminum and nickel in beta-NiAl(Pt) over the temperature range 1354 to 1692 K. These measurements were made with a multiple effusion-cell configured mass spectrometer (multi-cell KEMS). The results of this study show that Pt additions act to decreased alpha(Al) and increased the alpha(Ni) in beta-NiAl(Pt) for constant X(sub Ni)/X(sub Al) approx. = 1.13, while at constant X(sub Al) the affect of Pt on Al is greatly reduced. The measured partial enthalpies of mixing indicate Al-atoms have a strong self interaction while Ni- and Pt-atoms in have similar interactions with Al-atoms. Conversely the binding of Ni-atoms in beta-NiAl decreases with Pt addition independent of Al concentration. These initial results prove the technique can be applied to the Ni-Al-Pt system but more activity measurements are required to fully understand the thermodynamics of this system and how Pt additions improved the scaling behavior of nickel-based superalloys. In addition, with the choice of a suitable oxide material for the effusion-cell, the "closed" isothermal nature of the effusion-cell allows the direct investigation of an alloy-oxide equilibrium which resembles the "local-equilibrium" description of the metal-scale interface observed during high temperature oxidation. It is proposed that with an Al(l) + Al2O3(s) experimental reference state together with the route measurement of the relative partial-pressures of Al(g) and Al2O(g) allows the activities of O and Al2O3 to be determined along with the activities of Ni and Al. These measurements provide a direct method of investigating the thermodynamics of the metal-scale interface of a TGO-scale.

  4. Dissolved Divalent Metal and pH Effects on Amino Acid Polymerization: A Thermodynamic Evaluation.

    PubMed

    Kitadai, Norio

    2017-03-01

    Polymerization of amino acids is a fundamentally important step for the chemical evolution of life. Nevertheless, its response to changing environmental conditions has not yet been well understood because of the lack of reliable quantitative information. For thermodynamics, detailed prediction over diverse combinations of temperature and pH has been made only for a few amino acid-peptide systems. This study used recently reported thermodynamic dataset for the polymerization of the simplest amino acid "glycine (Gly)" to its short peptides (di-glycine and tri-glycine) to examine chemical and structural characteristics of amino acids and peptides that control the temperature and pH dependence of polymerization. Results showed that the dependency is strongly controlled by the intramolecular distance between the amino and carboxyl groups in an amino acid structure, although the side-chain group role is minor. The polymerization behavior of Gly reported earlier in the literature is therefore expected to be a typical feature for those of α-amino acids. Equilibrium calculations were conducted to examine effects of dissolved metals as a function of pH on the monomer-polymer equilibria of Gly. Results showed that metals shift the equilibria toward the monomer side, particularly at neutral and alkaline pH. Metals that form weak interaction with Gly (e.g., Mg(2+)) have no noticeable influence on the polymerization, although strong interaction engenders significant decrease of the equilibrium concentrations of Gly peptides. Considering chemical and structural characteristics of Gly and Gly peptides that control their interactions with metals, it can be expected that similar responses to the addition of metals are applicable in the polymerization of neutral α-amino acids. Neutral and alkaline aqueous environments with dissolved metals having high affinity with neutral α-amino acids (e.g., Cu(2+)) are therefore not beneficial places for peptide bond formation on the primitive

  5. Dissolved Divalent Metal and pH Effects on Amino Acid Polymerization: A Thermodynamic Evaluation

    NASA Astrophysics Data System (ADS)

    Kitadai, Norio

    2017-03-01

    Polymerization of amino acids is a fundamentally important step for the chemical evolution of life. Nevertheless, its response to changing environmental conditions has not yet been well understood because of the lack of reliable quantitative information. For thermodynamics, detailed prediction over diverse combinations of temperature and pH has been made only for a few amino acid-peptide systems. This study used recently reported thermodynamic dataset for the polymerization of the simplest amino acid "glycine (Gly)" to its short peptides (di-glycine and tri-glycine) to examine chemical and structural characteristics of amino acids and peptides that control the temperature and pH dependence of polymerization. Results showed that the dependency is strongly controlled by the intramolecular distance between the amino and carboxyl groups in an amino acid structure, although the side-chain group role is minor. The polymerization behavior of Gly reported earlier in the literature is therefore expected to be a typical feature for those of α-amino acids. Equilibrium calculations were conducted to examine effects of dissolved metals as a function of pH on the monomer-polymer equilibria of Gly. Results showed that metals shift the equilibria toward the monomer side, particularly at neutral and alkaline pH. Metals that form weak interaction with Gly (e.g., Mg2+) have no noticeable influence on the polymerization, although strong interaction engenders significant decrease of the equilibrium concentrations of Gly peptides. Considering chemical and structural characteristics of Gly and Gly peptides that control their interactions with metals, it can be expected that similar responses to the addition of metals are applicable in the polymerization of neutral α-amino acids. Neutral and alkaline aqueous environments with dissolved metals having high affinity with neutral α-amino acids (e.g., Cu2+) are therefore not beneficial places for peptide bond formation on the primitive

  6. Testing the Effects of Helium Pressurant on Thermodynamic Vent System Performance with Liquid Hydrogen

    NASA Technical Reports Server (NTRS)

    Flachbart, R. H.; Hastings, L. J.; Hedayat, A.; Nelson, S.; Tucker, S.

    2006-01-01

    In support of the development of a zero gravity pressure control capability for liquid hydrogen, testing was conducted at the Marshall Space Flight Center using the Multipurpose Hydrogen Test Bed (MHTB) to evaluate the effects of helium pressurant on the performance of a spray bar thermodynamic vent system (TVS). Fourteen days of testing was performed in August - September 2005, with an ambient heat leak of about 70-80 watts and tank fill levels of 90%, 50%, and 25%. The TVS successfully controlled the tank pressure within a +/- 3.45 kPa (+/- 0.5 psi) band with various helium concentration levels in the ullage. Relative to pressure control with an "all hydrogen" ullage, the helium presence resulted in 10 to 30 per cent longer pressure reduction durations, depending on the fill level, during the mixing/venting phase of the control cycle. Additionally, the automated control cycle was based on mixing alone for pressure reduction until the pressure versus time slope became positive, at which time the Joule-Thomson vent was opened. Testing was also conducted to evaluate thermodynamic venting without the mixer operating, first with liquid then with vapor at the recirculation line inlet. Although ullage stratification was present, the ullage pressure was successfully controlled without the mixer operating. Thus, if vapor surrounded the pump inlet in a reduced gravity situation, the ullage pressure can still be controlled by venting through the TVS Joule Thomson valve and heat exchanger. It was evident that the spray bar configuration, which extends almost the entire length of the tank, enabled significant thermal energy removal from the ullage even without the mixer operating. Details regarding the test setup and procedures are presented in the paper. 1

  7. Effects of Alloying on Nanoscale Grain Growth in Substitutional Binary Alloy System: Thermodynamics and Kinetics

    NASA Astrophysics Data System (ADS)

    Peng, Haoran; Chen, Yuzeng; Liu, Feng

    2015-11-01

    Applying the regular solution model, the Gibbs free energy of mixing for substitutional binary alloy system was constructed. Then, thermodynamic and kinetic parameters, e.g., driving force and solute drag force, controlling nanoscale grain growth of substitutional binary alloy systems were derived and compared to their generally accepted definitions and interpretations. It is suggested that for an actual grain growth process, the classical driving force P = γ/D ( γ the grain boundary (GB) energy, D the grain size) should be replaced by a new expression, i.e., P^' = γ /D - Δ P . Δ P represents the energy required to adjust nonequilibrium solute distribution to equilibrium solute distribution, which is equivalent to the generally accepted solute drag force impeding GB migration. By incorporating the derived new driving force for grain growth into the classical grain growth model, the reported grain growth behaviors of nanocrystalline Fe-4at. pct Zr and Pd-19at. pct Zr alloys were analyzed. On this basis, the effect of thermodynamic and kinetic parameters ( i.e., P, Δ P and the GB mobility ( M GB)) on nanoscale grain growth, were investigated. Upon grain growth, the decrease of P is caused by the reduction of γ as a result of solute segregation in GBs; the decrease of Δ P is, however, due to the decrease of grain growth velocity; whereas the decrease of M GB is attributed to the enhanced difference of solute molar fractions between the bulk and the GBs as well as the increased activation energy for GB diffusion.

  8. Life-history traits and effective population size in species with overlapping generations revisited: the importance of adult mortality.

    PubMed

    Waples, R S

    2016-10-01

    The relationship between life-history traits and the key eco-evolutionary parameters effective population size (Ne) and Ne/N is revisited for iteroparous species with overlapping generations, with a focus on the annual rate of adult mortality (d). Analytical methods based on populations with arbitrarily long adult lifespans are used to evaluate the influence of d on Ne, Ne/N and the factors that determine these parameters: adult abundance (N), generation length (T), age at maturity (α), the ratio of variance to mean reproductive success in one season by individuals of the same age (φ) and lifetime variance in reproductive success of individuals in a cohort (Vk•). Although the resulting estimators of N, T and Vk• are upwardly biased for species with short adult lifespans, the estimate of Ne/N is largely unbiased because biases in T are compensated for by biases in Vk• and N. For the first time, the contrasting effects of T and Vk• on Ne and Ne/N are jointly considered with respect to d and φ. A simple function of d and α based on the assumption of constant vital rates is shown to be a robust predictor (R(2)=0.78) of Ne/N in an empirical data set of life tables for 63 animal and plant species with diverse life histories. Results presented here should provide important context for interpreting the surge of genetically based estimates of Ne that has been fueled by the genomics revolution.

  9. High-throughput protein precipitation and hydrophobic interaction chromatography: salt effects and thermodynamic interrelation.

    PubMed

    Nfor, Beckley K; Hylkema, Nienke N; Wiedhaup, Koenraad R; Verhaert, Peter D E M; van der Wielen, Luuk A M; Ottens, Marcel

    2011-12-09

    Salt-induced protein precipitation and hydrophobic interaction chromatography (HIC) are two widely used methods for protein purification. In this study, salt effects in protein precipitation and HIC were investigated for a broad combination of proteins, salts and HIC resins. Interrelation between the critical thermodynamic salting out parameters in both techniques was equally investigated. Protein precipitation data were obtained by a high-throughput technique employing 96-well microtitre plates and robotic liquid handling technology. For the same protein-salt combinations, isocratic HIC experiments were performed using two or three different commercially available stationary phases-Phenyl Sepharose low sub, Butyl Sepharose and Resource Phenyl. In general, similar salt effects and deviations from the lyotropic series were observed in both separation methods, for example, the reverse Hofmeister effect reported for lysozyme below its isoelectric point and at low salt concentrations. The salting out constant could be expressed in terms of the preferential interaction parameter in protein precipitation, showing that the former is, in effect, the net result of preferential interaction of a protein with water molecules and salt ions in its vicinity. However, no general quantitative interrelation was found between salting out parameters or the number of released water molecules in protein precipitation and HIC. In other words, protein solubility and HIC retention factor could not be quantitatively interrelated, although for some proteins, regular trends were observed across the different resins and salt types.

  10. Effects of polydisperse crowders on aggregation reactions: A molecular thermodynamic analysis

    NASA Astrophysics Data System (ADS)

    Shah, Dhawal; Tan, Aik Lee; Ramakrishnan, Vigneshwar; Jiang, Jianwen; Rajagopalan, Raj

    2011-02-01

    Intracellular crowding in biological systems is usually mimicked in in vitro experiments by adding single crowders at high volume fractions, without taking into consideration the polydispersity of the crowders in the cellular environment. Here, we develop a molecular thermodynamic formalism to examine the effects of size-polydispersity of crowders on aggregation reaction equilibria. Although the predominantly common practice so far has been to appeal to the entropic (excluded-volume) effects in describing crowding effects, we show that the internal energy (hence, the enthalpy) of the system could dramatically alter the effects, even qualitatively, particularly in the case of a mixture of crowders, depending on the changes in the covolume of the products relative to that of the reactants and on the preferential binding or exclusion of the crowders by the reactants and products. We also show that in the case of polydisperse crowders the crowders with the largest size difference dominate the overall changes in the yield of the reaction, depending on the individual concentrations of the crowders.

  11. Effects of Macromolecular Crowding on Biochemical Reaction Equilibria: A Molecular Thermodynamic Perspective

    PubMed Central

    Hu, Zhongqiao; Jiang, Jianwen; Rajagopalan, Raj

    2007-01-01

    A molecular thermodynamic model is developed to investigate the effects of macromolecular crowding on biochemical reactions. Three types of reactions, representing protein folding/conformational isomerization, coagulation/coalescence, and polymerization/association, are considered. The reactants, products, and crowders are modeled as coarse-grained spherical particles or as polymer chains, interacting through hard-sphere interactions with or without nonbonded square-well interactions, and the effects of crowder size and chain length as well as product size are examined. The results predicted by this model are consistent with experimentally observed crowding effects based on preferential binding or preferential exclusion of the crowders. Although simple hard-core excluded-volume arguments do in general predict the qualitative aspects of the crowding effects, the results show that other intermolecular interactions can substantially alter the extent of enhancement or reduction of the equilibrium and can even change the direction of the shift. An advantage of the approach presented here is that competing reactions can be incorporated within the model. PMID:17513384

  12. Adsorption studies of Dichloromethane on some commercially available GACs: Effect of kinetics, thermodynamics and competitive ions.

    PubMed

    Khan, Moonis Ali; Kim, Seong-wook; Rao, Rifaqat Ali Khan; Abou-Shanab, R A I; Bhatnagar, Amit; Song, Hocheol; Jeon, Byong-Hun

    2010-06-15

    The objective of this work was to compare the effectiveness of four commercially available granular activated carbons (GACs); coconut (CGAC), wood (WGAC), lignite (LGAC) and bituminous (BGAC) for the removal of dichloromethane (DCM) from aqueous solution by batch process. Various parameters such as thermodynamics, kinetics, pH, concentration of adsorbate, dosages of adsorbent and competitive ions effect on DCM adsorption were investigated. Maximum adsorption capacity (45.5mg/g for CGAC) was observed at pH 6.0-8.0. The kinetics data indicate better applicability of pseudo-second-order kinetics model at 25 and 35 degrees C. Freundlich model was better obeyed on CGAC, WGAC, and BGAC, while LGAC followed Langmuir model. The adsorption process for 100mg/L initial DCM concentration on CGAC was exothermic in nature. The adsorption of DCM on various adsorbents involves physical adsorption process. The adsorption of DCM over a large range of initial concentration on CGAC and LGAC is effective even in presence of ionic salts.

  13. Thermodynamics and Cloud Radiative Effect from the First Year of GoAmazon

    NASA Technical Reports Server (NTRS)

    Collow, Allie Marquardt; Miller, Mark; Trabachino, Lynne

    2015-01-01

    Deforestation is an ongoing concern for the Amazon Rainforest of Brazil and associated changes to the land surface have been hypothesized to alter the climate in the region. A comprehensive set of meteorological observations at the surface and within the lower troposphere above Manacapuru, Brazil and data from the Modern Era Retrospective Analysis for Research and Applications Version 2 (MERRA-2) are used to evaluate the seasonal cycle of cloudiness, thermodynamics, and the radiation budget. While ample moisture is present in the Amazon Rainforest year round, the northward progression of the Hadley circulation during the dry season contributes to a drying of the middle troposphere and inhibits the formation of deep convection. This results in a reduction in cloudiness and precipitation as well as an increase in the height of the lifting condensation level, which is shown to have a negative correlation to the fraction of low clouds. Frequent cloudiness prevents solar radiation from reaching the surface and clouds are often reflective with high values of shortwave cloud radiative effect at the surface and top of the atmosphere. Cloud radiative effect is reduced during the dry season however the dry season surface shortwave cloud radiative effect is still double what is observed during the wet season in other tropical locations. Within the column, the impact of clouds on the radiation budget is more prevalent in the longwave part of the spectrum, with a net warming in the wet season.

  14. Effects of sulfur on lead partitioning during sludge incineration based on experiments and thermodynamic calculations

    SciTech Connect

    Liu, Jing-yong; Huang, Shu-jie; Sun, Shui-yu; Ning, Xun-an; He, Rui-zhe; Li, Xiao-ming; Chen, Tao; Luo, Guang-qian; Xie, Wu-ming; Wang, Yu-jie; Zhuo, Zhong-xu; Fu, Jie-wen

    2015-04-15

    Highlights: • A thermodynamic equilibrium calculation was carried out. • Effects of three types of sulfurs on Pb distribution were investigated. • The mechanism for three types of sulfurs acting on Pb partitioning were proposed. • Lead partitioning and species in bottom ash and fly ash were identified. - Abstract: Experiments in a tubular furnace reactor and thermodynamic equilibrium calculations were conducted to investigate the impact of sulfur compounds on the migration of lead (Pb) during sludge incineration. Representative samples of typical sludge with and without the addition of sulfur compounds were combusted at 850 °C, and the partitioning of Pb in the solid phase (bottom ash) and gas phase (fly ash and flue gas) was quantified. The results indicate that three types of sulfur compounds (S, Na{sub 2}S and Na{sub 2}SO{sub 4}) added to the sludge could facilitate the volatilization of Pb in the gas phase (fly ash and flue gas) into metal sulfates displacing its sulfides and some of its oxides. The effect of promoting Pb volatilization by adding Na{sub 2}SO{sub 4} and Na{sub 2}S was superior to that of the addition of S. In bottom ash, different metallic sulfides were found in the forms of lead sulfide, aluminosilicate minerals, and polymetallic-sulfides, which were minimally volatilized. The chemical equilibrium calculations indicated that sulfur stabilizes Pb in the form of PbSO{sub 4}(s) at low temperatures (<1000 K). The equilibrium calculation prediction also suggested that SiO{sub 2}, CaO, TiO{sub 2}, and Al{sub 2}O{sub 3} containing materials function as condensed phase solids in the temperature range of 800–1100 K as sorbents to stabilize Pb. However, in the presence of sulfur or chlorine or the co-existence of sulfur and chlorine, these sorbents were inactive. The effect of sulfur on Pb partitioning in the sludge incineration process mainly depended on the gas phase reaction, the surface reaction, the volatilization of products, and the

  15. Thermodynamic and kinetic size effects for hydrogen-desorption in catalytically-doped magnesium hydride: Nanoparticle versus bulk surface effects

    NASA Astrophysics Data System (ADS)

    Reich, Jason; Wang, L.-L.; Johnson, D. D.

    2010-03-01

    Using density-functional methods with simulated annealing, we show that there are no size effects for hydrogen desorption energies in nanoparticles (NPs) of MgH2. Recently reported exothermic desorption energies in MgH2-doped NP (Mg30XH62) are shown to be spurious, resulting from metastable NP configurations before dehyrogenation. We confirm that the 93-atom NPs are amorphous, with structures that are sensitive to the presence of dopants, found via simulated annealing techniques. We find that dehydrogenation energies are similar between bulk surfaces and nanoparticles, showing that the thermodynamics is unchanged by particle size as desorption is determined only by the local hydrogen-metal bond. We then discuss the effects of nanoparticle size and presence of dopants on the kinetic barriers between NPs and bulk surfaces. The takehome message is: In modeling desorption events, especially within amorphous NPs, metastable, local minimum must be carefully avoided, and, in doing so, an accurate and physically reasonable picture emerges for the thermodynamic and kinetic behavior.

  16. Thermodynamic estimation: Ionic materials

    SciTech Connect

    Glasser, Leslie

    2013-10-15

    Thermodynamics establishes equilibrium relations among thermodynamic parameters (“properties”) and delineates the effects of variation of the thermodynamic functions (typically temperature and pressure) on those parameters. However, classical thermodynamics does not provide values for the necessary thermodynamic properties, which must be established by extra-thermodynamic means such as experiment, theoretical calculation, or empirical estimation. While many values may be found in the numerous collected tables in the literature, these are necessarily incomplete because either the experimental measurements have not been made or the materials may be hypothetical. The current paper presents a number of simple and relible estimation methods for thermodynamic properties, principally for ionic materials. The results may also be used as a check for obvious errors in published values. The estimation methods described are typically based on addition of properties of individual ions, or sums of properties of neutral ion groups (such as “double” salts, in the Simple Salt Approximation), or based upon correlations such as with formula unit volumes (Volume-Based Thermodynamics). - Graphical abstract: Thermodynamic properties of ionic materials may be readily estimated by summation of the properties of individual ions, by summation of the properties of ‘double salts’, and by correlation with formula volume. Such estimates may fill gaps in the literature, and may also be used as checks of published values. This simplicity arises from exploitation of the fact that repulsive energy terms are of short range and very similar across materials, while coulombic interactions provide a very large component of the attractive energy in ionic systems. Display Omitted - Highlights: • Estimation methods for thermodynamic properties of ionic materials are introduced. • Methods are based on summation of single ions, multiple salts, and correlations. • Heat capacity, entropy

  17. Thermodynamic and mechanical effects of disulfide bonds in CXCLl7 chemokine

    NASA Astrophysics Data System (ADS)

    Singer, Christopher

    Chemokines are a family of signaling proteins mainly responsible for the chemotaxis of leukocytes, where their biological activity is modulated by their oligomerization state. Here, the dynamics and thermodynamic stability are characterized in monomer and homodimer structures of CXCL7, one of the most abundant platelet chemokines. The effects of dimerization and disulfide bond formation are investigated using computational methods that include molecular dynamics (MD) simulations and the Distance Constraint Model (DCM). A consistent picture emerges for the effect of dimerization and role of the Cys5-Cys31 and Cys7- Cys47 disulfide bonds. Surprisingly, neither disulfide bond is critical for maintaining structural stability in the monomer or dimer, although the monomer is destabilized more than the dimer upon removal of disulfide bonds. Instead, it is found that disulfide bonds influence the native state dynamics as well as modulates the relative stability between monomer and dimer. The combined analysis elucidates how CXCL7 is mechanically stable as a monomer, and how upon dimerization flexibly correlated motions are induced between the 30s and 50s loop within each monomer and across the dimer interface. Interestingly, the greatest gain in flexibility upon dimerization occurs when both disulfide bonds are present in each domain, and the homodimer is least stable relative to its two monomers. These results suggest the highly conserved disulfide bonds in chemokines facilitate a structural mechanism for distinguishing functional characteristics between monomer and dimer.

  18. Water-membrane partition thermodynamics of an amphiphilic lipopeptide: an enthalpy-driven hydrophobic effect.

    PubMed

    Gorfe, Alemayehu A; Baron, Riccardo; McCammon, J Andrew

    2008-10-01

    To shed light on the driving force for the hydrophobic effect that partitions amphiphilic lipoproteins between water and membrane, we carried out an atomically detailed thermodynamic analysis of a triply lipid modified H-ras heptapeptide anchor (ANCH) in water and in a DMPC (1,2-dimyristoyl-sn-glycero-3-phosphocholine) bilayer. Combining molecular mechanical and continuum solvent approaches with an improved technique for solute entropy calculation, we obtained an overall transfer free energy of approximately -13 kcal mol(-1). This value is in qualitative agreement with free energy changes derived from a potential of mean force calculation and indirect experimental observations. Changes in free energies of solvation and ANCH conformational reorganization are unfavorable, whereas ANCH-DMPC interactions-especially van der Waals-favor insertion. These results are consistent with an enthalpy-driven hydrophobic effect, in accord with earlier calorimetric data on the membrane partition of other amphiphiles. Furthermore, structural and entropic analysis of molecular dynamics-generated ensembles suggests that conformational selection may play a hitherto unappreciated role in membrane insertion of lipid-modified peptides and proteins.

  19. Computationally efficient determination of hydrogen isotope effects on the thermodynamic stability of metal hydrides

    NASA Astrophysics Data System (ADS)

    Nicholson, Kelly M.; Sholl, David S.

    2012-10-01

    Although the thermodynamics of metal hydrides at low to moderate temperatures has been successfully described with density functional theory (DFT) calculations using 0 K total energies and simple harmonic models, it is unclear if this approach is valid for hydrides that are stable at high temperatures. To aid development of computationally efficient methods, this paper uses DFT to explore the predicted stabilities of ZrH2, HfH2, TiH2, LiH, and NaH with four levels of theory. We also investigate isotope effects to understand if these should be accounted for in screening of deuterated or tritiated materials. We show that calculations that account for vibrational corrections to the crystal lattice are not necessary to get an accurate description of relative stabilities of metal hydrides. The shifts in dissociation temperatures due to isotope substitutions are <50 K for all materials, with larger shifts for lighter materials, as expected. We show that accounting for vibrational effects due to isotope substitution in metal hydrides is unnecessary to accurately predict the relative stabilities of metal hydrides at high temperatures.

  20. Effect of heating strategies on whey protein denaturation--Revisited by liquid chromatography quadrupole time-of-flight mass spectrometry.

    PubMed

    Akkerman, M; Rauh, V M; Christensen, M; Johansen, L B; Hammershøj, M; Larsen, L B

    2016-01-01

    Previous standards in the area of effect of heat treatment processes on milk protein denaturation were based primarily on laboratory-scale analysis and determination of denaturation degrees by, for example, electrophoresis. In this study, whey protein denaturation was revisited by pilot-scale heating strategies and liquid chromatography quadrupole time-of-flight mass spectrometer (LC/MC Q-TOF) analysis. Skim milk was heat treated by the use of 3 heating strategies, namely plate heat exchanger (PHE), tubular heat exchanger (THE), and direct steam injection (DSI), under various heating temperatures (T) and holding times. The effect of heating strategy on the degree of denaturation of β-lactoglobulin and α-lactalbumin was determined using LC/MC Q-TOF of pH 4.5-soluble whey proteins. Furthermore, effect of heating strategy on the rennet-induced coagulation properties was studied by oscillatory rheometry. In addition, rennet-induced coagulation of heat-treated micellar casein concentrate subjected to PHE was studied. For skim milk, the whey protein denaturation increased significantly as T and holding time increased, regardless of heating method. High denaturation degrees were obtained for T >100°C using PHE and THE, whereas DSI resulted in significantly lower denaturation degrees, compared with PHE and THE. Rennet coagulation properties were impaired by increased T and holding time regardless of heating method, although DSI resulted in less impairment compared with PHE and THE. No significant difference was found between THE and PHE for effect on rennet coagulation time, whereas the curd firming rate was significantly larger for THE compared with PHE. Micellar casein concentrate possessed improved rennet coagulation properties compared with skim milk receiving equal heat treatment.

  1. The super greenhouse effect in a warming world: the role of dynamics and thermodynamics

    NASA Astrophysics Data System (ADS)

    Kashinath, Karthik; O'Brien, Travis; Collins, William

    2016-04-01

    Over warm tropical oceans the increase in greenhouse trapping with increasing SST can be faster than that of the surface emission, resulting in a decrease in clear sky outgoing longwave radiation at the top of the atmosphere (OLR) when SST increases, also known as the super greenhouse effect (SGE). If the SGE is directly linked to SST changes, there are profound implications for positive climate feedbacks in the tropics. We show that CMIP5 models perform well in simulating the observed clear-sky greenhouse effect in the present day. Using global warming experiments we show that the onset and shutdown SST of the SGE, as well as the magnitude of the SGE, increase as the convective threshold SST increases. To account for an increasing convective threshold SST we use an invariant coordinate for convection proposed in a recent study [Williams et al., GRL (2009)]. However, even after accounting for the increase in tropical SST (by normalizing the SGE by surface emission) and accounting for the increase in the threshold temperature for convection (by using the invariant coordinate) we find that the models predict a distinct increase in the clear-sky greenhouse effect in a warmed world. This suggests that thermodynamics (i.e. SST) plays a crucial role in regulating the increasing clear sky greenhouse effect in a warming world. We use theoretical arguments to estimate this increase in SGE and derive its dependence on SST. Finally, as shown in previous studies, we confirm that the increase in the clear-sky greenhouse effect is primarily due to upper tropospheric moistening. Although the absolute increase in upper tropospheric water vapor is small compared to that of the lower troposphere, since the absorptivity scales with fractional changes in water vapor, the contribution of the upper troposphere is more significant, as shown by Chung et al., PNAS (2014).

  2. The effects of thermodynamic stability on wind properties in different low-mass black hole binary states

    NASA Astrophysics Data System (ADS)

    Chakravorty, Susmita; Lee, Julia C.; Neilsen, Joseph

    2013-11-01

    We present a systematic theory-motivated study of the thermodynamic stability condition as an explanation for the observed accretion disc wind signatures in different states of low-mass black hole binaries (BHB). The variability in observed ions is conventionally explained either by variations in the driving mechanisms or by the changes in the ionizing flux or due to density effects, whilst thermodynamic stability considerations have been largely ignored. It would appear that the observability of particular ions in different BHB states can be accounted for through simple thermodynamic considerations in the static limit. Our calculations predict that in the disc-dominated soft thermal and intermediate states, the wind should be thermodynamically stable and hence observable. On the other hand, in the power-law-dominated spectrally hard state the wind is found to be thermodynamically unstable for a certain range of 3.55 ≤ log ξ ≤ 4.20. In the spectrally hard state, a large number of the He-like and H-like ions (including e.g. Fe XXV, Ar XVIII and S XV) have peak ion fractions in the unstable ionization parameter (ξ) range, making these ions undetectable. Our theoretical predictions have clear corroboration in the literature reporting differences in wind ion observability as the BHBs transition through the accretion states While this effect may not be the only one responsible for the observed gradient in the wind properties as a function of the accretion state in BHBs, it is clear that its inclusion in the calculations is crucial for understanding the link between the environment of the compact object and its accretion processes.

  3. Revisiting the role of global SST anomalies and their effects on West African monsoon variability

    NASA Astrophysics Data System (ADS)

    Pomposi, Catherine; Kushnir, Yochanan; Giannini, Alessandra

    2016-04-01

    The West African Monsoon is a significant component of the global monsoon system, delivering the majority of annual precipitation for the Sahel and varying on timescales from seasons to decades and beyond. Much of the internal variability of this system is driven by sea surface temperature (SST) anomalies and their resulting atmospheric teleconnections linking oceanic changes to land-based precipitation. Previous idealized studies have identified the role of particular ocean basins in driving monsoon variations on a number of key timescales, including the Atlantic basin as the main driver behind decadal-scale changes and the Pacific basin for interannual variability. However, understanding of how the monsoon responds to global SSTs remains incomplete because the system can be affected by moisture availability locally as well as tropical atmospheric stability, both of which are influenced by ocean temperatures. Furthermore, the complexity of how the global ocean basins change in relation to one another (what we refer to as superposition of anomalies) can result in Sahel precipitation anomalies that are contrary to what one might posit when considering the state of a single basin alone (e.g. the 2015 El Niño event and a relatively wet Sahel). The aim of this work is to revisit the role of global SSTs in driving Sahel rainfall variability over the recent past using a blending of observations and new model output. We seek to disentangle the state of various basins in combination with each other in driving normal or anomalously dry or wet years, resolving the ways that remote and local ocean forcings affect the movement of convection from the Guinea coast inland and northward into the Sahel, and include the study of circulation and stability components of the atmosphere. Preliminary diagnostic work suggests that varying SST conditions across ocean basins could imprint distinctly different precipitation responses in the Sahel. For example, precipitation anomalies are

  4. Thermodynamical effects accompanied freezing of two water layers separated by sea ice sheet

    NASA Astrophysics Data System (ADS)

    Bogorodsky, Petr; Marchenko, Aleksey

    2014-05-01

    The process of melt pond freezing is very important for generation of sea ice cover thermodynamic and mass balance during winterperiod. However, due to significant difficulties of field measurements the available data of model estimations still have no instrumental confirmation. In May 2009 the authors carried out laboratory experiment on freezing of limited water volume in the University Centre in Svalbard ice tank. In the course of experiment fresh water layer of 27.5 cm thickness at freezing point poured on the 24 cm sea ice layer was cooled during 50 hours at the temperature -10º C and then once again during 60 hours at -20º C. For revealing process typical characteristics the data of continuous measurements of temperature and salinity in different phases were compared with data of numerical computations obtained with thermodynamic model which was formulated in the frames of 1-D equation system (infinite extension of water freezing layer) and adapted to laboratory conditions. The known surprise of the experiment became proximity of calculated and measured estimates of process dynamics that confirmed the adequacy of the problem mathematical statement (excluding probably process finale stage). This effect can be explained by formation of cracks on the upper layer of ice at sharp decreases of air temperature, which temporary compensated hydrostatic pressure growth during freezing of closed water volume. Another compensated mechanism can be migration of brine through the lower layer of ice under influence of vertical pressure gradient and also rejection of gas dissolved in water which increased its compressibility. During 110 hours cooling thickness of water layer between ice layers reduced approximately to 2 cm. According to computations this layer is not chilled completely but keeps as thin brine interlayer within ice body whose thickness (about units of mm) is determined by temperature fluctuations of cooled surface. Nevertheless, despite good coincidence of

  5. Natural Gas Evolution in a Gas Hydrate Melt: Effect of Thermodynamic Hydrate Inhibitors.

    PubMed

    Sujith, K S; Ramachandran, C N

    2017-01-12

    Natural gas extraction from gas hydrate sediments by injection of hydrate inhibitors involves the decomposition of hydrates. The evolution of dissolved gas from the hydrate melt is an important step in the extraction process. Using classical molecular dynamics simulations, we study the evolution of dissolved methane from its hydrate melt in the presence of two thermodynamic hydrate inhibitors, NaCl and CH3OH. An increase in the concentration of hydrate inhibitors is found to promote the nucleation of methane nanobubbles in the hydrate melt. Whereas NaCl promotes bubble formation by enhancing the hydrophobic interaction between aqueous CH4 molecules, CH3OH molecules assist bubble formation by stabilizing CH4 bubble nuclei formed in the solution. The CH3OH molecules accumulate around the nuclei leading to a decrease in the surface tension at their interface with water. The nanobubbles formed are found to be highly dynamic with frequent exchange of CH4 molecules between the bubble and the surrounding liquid. A quantitative analysis of the dynamic behavior of the bubble is performed by introducing a unit step function whose value depends on the location of CH4 molecules with respect to the bubble. It is observed that an increase in the concentration of thermodynamic hydrate inhibitors reduces the exchange process, making the bubble less dynamic. It is also found that for a given concentration of the inhibitor, larger bubbles are less dynamic compared to smaller ones. The dependence of the dynamic nature of nanobubbles on bubble size and inhibitor concentration is correlated with the solubility of CH4 and the Laplace pressure within the bubble. The effect of CO2 on the formation of nanobubble in the CH4-CO2 mixed gas hydrate melt in the presence of inhibitors is also examined. The simulations show that the presence of CO2 molecules significantly reduces the induction time for methane nanobubble nucleation. The role of CO2 in the early nucleation of bubble is explained

  6. pH effect on protein G orientation on gold surfaces and characterization of adsorption thermodynamics.

    PubMed

    Johnson, Blake N; Mutharasan, Raj

    2012-05-01

    The pH effect on adsorbed antibody-binding protein (protein G) orientation on gold (Au) and its adsorption thermodynamic characteristics were investigated using quartz crystal microbalance (QCM) and X-ray photoelectron spectroscopy (XPS). The adsorbed protein G orientation was measured by binding response of two antibody-antigen systems: the model bovine serum albumin (BSA) and the foodborne pathogen E. coli O157:H7. Surface coverage was not significantly affected by pH, but its orientation was. The most properly oriented protein G for antibody binding was achieved at near-neutral pH. Adsorption was verified by XPS measurements using nitrogen (N) 1s, oxygen (O) 1s, and Au 4p peak heights. Adsorption energetics were determined by van't Hoff and Langmuir kinetic analyses of adsorption data obtained at 296, 303, and 308 K. Large characteristic entropy change of protein adsorption was observed (ΔS° = 0.52 ± 0.01 kcal/mol·K). The adsorption process was not classical physisorption but exhibited chemisorption characteristics based on significant enthalpy change (ΔH° = -25 ± 6 kcal/mol).

  7. Effect of thermodynamic disequilibrium on critical liquid-vapor flow conditions

    SciTech Connect

    Bilicki, Z.; Kestin, J.

    1989-01-01

    In this lecture we characterize the effect of absence of unconstrained thermodynamic equilibrium and onset of a metastable state on the adiabatic flow of a mixture of liquid and its vapor through a convergent-divergent nozzle. We study steady-state flows and emphasize the relations that are present when the flow is choked. In such cases, there exists a cross-section in which the flow is critical and in which the adiabatic wave of small amplitude is stationary. More precisely, the relaxation process which results from the lack of equilibrium causes the system to be dispersive. In such circumstances, the critical velocity is equal to the frozen speed of sound, a/sub f/ corresponding to /omega/ /yields/ /infinity/. The relaxation process displaces the critical cross-section quite far downstream from the throat and places it in the divergent portion of the channel. We present the topological portrait of solutions in a suitably defined state-velocity space and discuss the potential appearance of normal and dispersed shock waves. In extreme cases, the singular point (usually a saddle) which enables the flow to become supercritical is displaced so far that it is located outside the exit. Then, the flow velocity is everywhere subcritical (w < a/sub f/) even though it may exceed the equilibrium speed of sound (w /approx gt/ a/sub e/) beyond a certain cross-section, and in spite of the presence of a throat. 10 refs., 4 figs.

  8. Thermodynamic, spectroscopic, and computational studies of lanthanide complexation with Diethylenetriaminepentaacetic acide: temperature effect and coordination modes

    SciTech Connect

    Guoxin Tian; Leigh R. Martin; Zhiyong Zhang; Linfeng Rao

    2011-04-01

    Stability constants of two DTPA (diethylenetriaminepentaacetic acid) complexes with lanthanides (ML2- and MHL-, where M stands for Nd and Eu and L stands for diethylenetriaminepentaacetate) at 10, 25, 40, 55, and 70 degrees C were determined by potentiometry, absorption spectrophotometry, and luminescence spectroscopy. The enthalpies of complexation at 25 degrees C were determined by microcalorimetry. Thermodynamic data show that the complexation of Nd3þ and Eu3þ with DTPA is weakened at higher temperatures, a 10-fold decrease in the stability constants of ML2- and MHL- as the temperature is increased from 10 to 70 degrees C. The effect of temperature is consistent with the exothermic enthalpy of complexation directly measured by microcalorimetry. Results by luminescence spectroscopy and density functional theory (DFT) calculations suggest that DTPA is octa-dentate in both the EuL2- and EuHL- complexes and, for the first time, the coordination mode in the EuHL- complex was clarified by integration of the experimental data and DFT calculations. In the EuHL- complex, the Eu is coordinated by an octa-dentate H(DTPA) ligand and a water molecule, and the protonation occurs on the oxygen of a carboxylate group.

  9. Effect of hydration on structural and thermodynamic properties of pig gastric and bovine submaxillary gland mucins.

    PubMed

    Znamenskaya, Yana; Sotres, Javier; Engblom, Johan; Arnebrant, Thomas; Kocherbitov, Vitaly

    2012-04-26

    One of the essential functions of mucous gel is protection of tissues against dehydration. The effect of hydration on the structural and thermodynamic properties of pig gastric mucin (PGM) and bovine submaxillary gland mucin (BSM) have been studied using atomic force microscopy (AFM), sorption, and differential scanning calorimetry (DSC). The analysis of sorption isotherms shows the higher water sorption capacity of PGM compared to BSM at RH levels lower than about 78%. The value of the hydration enthalpy at zero water content at 25 °C for both biopolymers is about -20 kJ/mol. Glass transitions of BSM and PGM occur at RH levels between 60 and 70% for both mucins. AFM indicates the presence of a dumbbell structure as well as a fiber-like structure in PGM samples. The experimental volume of the dry dumbbell molecule obtained by AFM is 3140 ± 340 nm(3). Using DSC data, the amount of nonfreezing water was calculated to be about 0.51 g/g of PGM. The phase diagram of PGM demonstrates two regions of different Tg: dependent and independent of hydration levels. In particular, at mucin concentrations from 0 to 67 wt %, the glass transition occurs at a constant temperature of about -15 °C. At higher concentrations of mucin, Tg is increasing with increasing mucin concentrations.

  10. Thermodynamic holography

    NASA Astrophysics Data System (ADS)

    Wei, Bo-Bo; Jiang, Zhan-Feng; Liu, Ren-Bao

    2015-10-01

    The holographic principle states that the information about a volume of a system is encoded on the boundary surface of the volume. Holography appears in many branches of physics, such as optics, electromagnetism, many-body physics, quantum gravity, and string theory. Here we show that holography is also an underlying principle in thermodynamics, a most important foundation of physics. The thermodynamics of a system is fully determined by its partition function. We prove that the partition function of a finite but arbitrarily large system is an analytic function on the complex plane of physical parameters, and therefore the partition function in a region on the complex plane is uniquely determined by its values along the boundary. The thermodynamic holography has applications in studying thermodynamics of nano-scale systems (such as molecule engines, nano-generators and macromolecules) and provides a new approach to many-body physics.

  11. Molecular-crowding effects on single-molecule RNA folding/unfolding thermodynamics and kinetics.

    PubMed

    Dupuis, Nicholas F; Holmstrom, Erik D; Nesbitt, David J

    2014-06-10

    The effects of "molecular crowding" on elementary biochemical processes due to high solute concentrations are poorly understood and yet clearly essential to the folding of nucleic acids and proteins into correct, native structures. The present work presents, to our knowledge, first results on the single-molecule kinetics of solute molecular crowding, specifically focusing on GAAA tetraloop-receptor folding to isolate a single RNA tertiary interaction using time-correlated single-photon counting and confocal single-molecule FRET microscopy. The impact of crowding by high-molecular-weight polyethylene glycol on the RNA folding thermodynamics is dramatic, with up to ΔΔG° ∼ -2.5 kcal/mol changes in free energy and thus >60-fold increase in the folding equilibrium constant (Keq) for excluded volume fractions of 15%. Most importantly, time-correlated single-molecule methods permit crowding effects on the kinetics of RNA folding/unfolding to be explored for the first time (to our knowledge), which reveal that this large jump in Keq is dominated by a 35-fold increase in tetraloop-receptor folding rate, with only a modest decrease in the corresponding unfolding rate. This is further explored with temperature-dependent single-molecule RNA folding measurements, which identify that crowding effects are dominated by entropic rather than enthalpic contributions to the overall free energy change. Finally, a simple "hard-sphere" treatment of the solute excluded volume is invoked to model the observed kinetic trends, and which predict ΔΔG° ∼ -5 kcal/mol free-energy stabilization at excluded volume fractions of 30%.

  12. Revisiting the effect of maternal smoking during pregnancy on offspring birthweight: a quasi-experimental sibling analysis in Sweden.

    PubMed

    Juárez, Sol Pía; Merlo, Juan

    2013-01-01

    Maternal smoking during pregnancy (SDP) seems associated with reduced birthweight in the offspring. This observation, however, is based on conventional epidemiological analyses, and it might be confounded by unobserved maternal characteristics related to both smoking habits and offspring birth weight. Therefore, we apply a quasi-experimental sibling analysis to revisit previous findings. Using the Swedish Medical Birth Register, we identified 677,922 singletons born between 2002 and 2010 from native Swedish mothers. From this population, we isolated 62,941 siblings from 28,768 mothers with discrepant habits of SDP. We applied conventional and mother-specific multilevel linear regression models to investigate the association between maternal SDP and offspring birthweight. Depending on the mother was light or heavy smoker and the timing of exposition during pregnancy (i.e., first or third trimester), the effect of smoking on birthweight reduction was between 6 and 78 g less marked in the sibling analysis than in the conventional analysis. Sibling analysis showed that continuous smoking reduces birthweight by 162 grams for mothers who were light smokers (1 to 9 cigarettes per day) and 226 g on average for those who were heavy smokers throughout the pregnancy in comparison to non-smoker mothers. Quitting smoking during pregnancy partly counteracted the smoking-related birthweight reduction by 1 to 29 g, and a subsequent smoking relapse during pregnancy reduced birthweight by 77 to 83 g. The sibling analysis provides strong evidence that maternal SDP reduces offspring birthweight, though this reduction was not as great as that observed in the conventional analysis. Our findings support public health interventions aimed to prevent SDP and to persuade those who already smoke to quit and not relapse throughout the pregnancy. Besides, further analyses are needed in order to explain the mechanisms through which smoking reduces birthweight and to identify other maternal

  13. Assessing nanoparticle size effects on metal hydride thermodynamics using the Wulff construction.

    PubMed

    Kim, Ki Chul; Dai, Bing; Karl Johnson, J; Sholl, David S

    2009-05-20

    The reaction thermodynamics of metal hydrides are crucial to the use of these materials for reversible hydrogen storage. In addition to altering the kinetics of metal hydride reactions, the use of nanoparticles can also change the overall reaction thermodynamics. We use density functional theory to predict the equilibrium crystal shapes of seven metals and their hydrides via the Wulff construction. These calculations allow the impact of nanoparticle size on the thermodynamics of hydrogen release from these metal hydrides to be predicted. Specifically, we study the temperature required for the hydride to generate a H(2) pressure of 1 bar as a function of the radius of the nanoparticle. In most, but not all, cases the hydrogen release temperature increases slightly as the particle size is reduced.

  14. Stochastic thermodynamics

    NASA Astrophysics Data System (ADS)

    Eichhorn, Ralf; Aurell, Erik

    2014-04-01

    'Stochastic thermodynamics as a conceptual framework combines the stochastic energetics approach introduced a decade ago by Sekimoto [1] with the idea that entropy can consistently be assigned to a single fluctuating trajectory [2]'. This quote, taken from Udo Seifert's [3] 2008 review, nicely summarizes the basic ideas behind stochastic thermodynamics: for small systems, driven by external forces and in contact with a heat bath at a well-defined temperature, stochastic energetics [4] defines the exchanged work and heat along a single fluctuating trajectory and connects them to changes in the internal (system) energy by an energy balance analogous to the first law of thermodynamics. Additionally, providing a consistent definition of trajectory-wise entropy production gives rise to second-law-like relations and forms the basis for a 'stochastic thermodynamics' along individual fluctuating trajectories. In order to construct meaningful concepts of work, heat and entropy production for single trajectories, their definitions are based on the stochastic equations of motion modeling the physical system of interest. Because of this, they are valid even for systems that are prevented from equilibrating with the thermal environment by external driving forces (or other sources of non-equilibrium). In that way, the central notions of equilibrium thermodynamics, such as heat, work and entropy, are consistently extended to the non-equilibrium realm. In the (non-equilibrium) ensemble, the trajectory-wise quantities acquire distributions. General statements derived within stochastic thermodynamics typically refer to properties of these distributions, and are valid in the non-equilibrium regime even beyond the linear response. The extension of statistical mechanics and of exact thermodynamic statements to the non-equilibrium realm has been discussed from the early days of statistical mechanics more than 100 years ago. This debate culminated in the development of linear response

  15. Mg/Ca ratios in freshwater microbial carbonates: Thermodynamic, kinetic and vital effects

    NASA Astrophysics Data System (ADS)

    Saunders, P.; Rogerson, M.; Wadhawan, J. D.; Greenway, G.; Pedley, H. M.

    2014-12-01

    The ratio of magnesium to calcium (Mg/Ca) in carbonate minerals in an abiotic setting is conventionally assumed to be predominantly controlled by (Mg/Ca)solution and a temperature dependant partition coefficient. This temperature dependence suggests that both marine (e.g. foraminiferal calcite and corals) and freshwater (e.g. speleothems and surface freshwater deposits, “tufas”) carbonate deposits may be important archives of palaeotemperature data. However, there is considerable uncertainty in all these settings. In surface freshwater deposits this uncertainty is focussed on the influence of microbial biofilms. Biogenic or “vital” effects may arise from microbial metabolic activity and/or the presence of extracellular polymeric substances (EPS). This study addresses this key question for the first time, via a series of unique through-flow microcosm and agitated flask experiments where freshwater calcite was precipitated under controlled conditions. These experiments reveal there is no strong relationship between (Mg/Ca)calcite and temperature, so the assumption of thermodynamic fractionation is not viable. However, there is a pronounced influence on (Mg/Ca)calcite from precipitation rate, so that rapidly forming precipitates develop with very low magnesium content indicating kinetic control on fractionation. Calcite precipitation rate in these experiments (where the solution is only moderately supersaturated) is controlled by biofilm growth rate, but occurs even when light is excluded indicating that photosynthetic influences are not critical. Our results thus suggest the apparent kinetic fractionation arises from the electrochemical activity of EPS molecules, and are therefore likely to occur wherever these molecules occur, including stromatolites, soil and lake carbonates and (via colloidal EPS) speleothems.

  16. The effect of composition and thermodynamics on the surface morphology of durable superhydrophobic polymer coatings.

    PubMed

    Nahum, Tehila; Dodiuk, Hanna; Kenig, Samuel; Panwar, Artee; Barry, Carol; Mead, Joey

    2017-01-01

    Durable superhydrophobic coatings were synthesized using a system of silica nanoparticles (NPs) to provide nanoscale roughness, fluorosilane to give hydrophobic chemistry, and three different polymer binders: urethane acrylate, ethyl 2-cyanoacrylate, and epoxy. Coatings composed of different binders incorporating NPs in various concentrations exhibited different superhydrophobic attributes when applied on polycarbonate (PC) and glass substrates and as a function of coating composition. It was found that the substrate surface characteristics and wettability affected the superhydrophobic characteristics of the coatings. Interfacial tension and spreading coefficient parameters (thermodynamics) of the coating components were used to predict the localization of the NPs for the different binders' concentrations. The thermodynamic analysis of the NPs localization was in good agreement with the experimental observations. On the basis of the thermodynamic analysis and the experimental scanning electron microscopy, X-ray photoelectron spectroscopy, profilometry, and atomic force microscopy results, it was concluded that localization of the NPs on the surface was critical to provide the necessary roughness and resulting superhydrophobicity. The durability evaluated by tape testing of the epoxy formulations was the best on both glass and PC. Several coating compositions retained their superhydrophobicity after the tape test. In summary, it was concluded that thermodynamic analysis is a powerful tool to predict the roughness of the coating due to the location of NPs on the surface, and hence can be used in the design of superhydrophobic coatings.

  17. Thermodynamics of superstring on near-extremal NS5 and effective Hagedorn behavior

    NASA Astrophysics Data System (ADS)

    Sugawara, Yuji

    2012-10-01

    We study the thermodynamical torus partition function of superstring on the near-extremal black NS5-brane background. The exact partition function has been computed with the helps of our previous works: [arXiv:1012.5721 [hep-th

  18. The effect of composition and thermodynamics on the surface morphology of durable superhydrophobic polymer coatings

    PubMed Central

    Nahum, Tehila; Dodiuk, Hanna; Kenig, Samuel; Panwar, Artee; Barry, Carol; Mead, Joey

    2017-01-01

    Durable superhydrophobic coatings were synthesized using a system of silica nanoparticles (NPs) to provide nanoscale roughness, fluorosilane to give hydrophobic chemistry, and three different polymer binders: urethane acrylate, ethyl 2-cyanoacrylate, and epoxy. Coatings composed of different binders incorporating NPs in various concentrations exhibited different superhydrophobic attributes when applied on polycarbonate (PC) and glass substrates and as a function of coating composition. It was found that the substrate surface characteristics and wettability affected the superhydrophobic characteristics of the coatings. Interfacial tension and spreading coefficient parameters (thermodynamics) of the coating components were used to predict the localization of the NPs for the different binders’ concentrations. The thermodynamic analysis of the NPs localization was in good agreement with the experimental observations. On the basis of the thermodynamic analysis and the experimental scanning electron microscopy, X-ray photoelectron spectroscopy, profilometry, and atomic force microscopy results, it was concluded that localization of the NPs on the surface was critical to provide the necessary roughness and resulting superhydrophobicity. The durability evaluated by tape testing of the epoxy formulations was the best on both glass and PC. Several coating compositions retained their superhydrophobicity after the tape test. In summary, it was concluded that thermodynamic analysis is a powerful tool to predict the roughness of the coating due to the location of NPs on the surface, and hence can be used in the design of superhydrophobic coatings. PMID:28243071

  19. An Easy and Effective Demonstration of Enzyme Stereospecificity and Equilibrium Thermodynamics

    ERIC Educational Resources Information Center

    Herdman, Chelsea; Dickman, Michael

    2011-01-01

    Enzyme stereospecificity and equilibrium thermodynamics can be demonstrated using the coupling of two amino acid derivatives by Thermoase C160. This protease will catalyze peptide bond formation between Z-L-AspOH and L-PheOMe to form the Aspartame precursor Z-L-Asp-L-PheOMe. Reaction completion manifests itself by precipitation of the product. As…

  20. The Effectiveness of Problem-Based Learning on Teaching the First Law of Thermodynamics

    ERIC Educational Resources Information Center

    Tatar, Erdal; Oktay, Munir

    2011-01-01

    Background: Problem-based learning (PBL) is a teaching approach working in cooperation with self-learning and involving research to solve real problems. The first law of thermodynamics states that energy can neither be created nor destroyed, but that energy is conserved. Students had difficulty learning or misconceptions about this law. This study…

  1. COMPUTER SIMULATIONS WITH EXPLICIT SOLVENT: Recent Progress in the Thermodynamic Decomposition of Free Energies and in Modeling Electrostatic Effects

    NASA Astrophysics Data System (ADS)

    Levy, Ronald M.; Gallicchio, Emilio

    1998-10-01

    This review focuses on recent progress in two areas in which computer simulations with explicit solvent are being applied: the thermodynamic decomposition of free energies, and modeling electrostatic effects. The computationally intensive nature of these simulations has been an obstacle to the systematic study of many problems in solvation thermodynamics, such as the decomposition of solvation and ligand binding free energies into component enthalpies and entropies. With the revolution in computer power continuing, these problems are ripe for study but require the judicious choice of algorithms and approximations. We provide a critical evaluation of several numerical approaches to the thermodynamic decomposition of free energies and summarize applications in the current literature. Progress in computer simulations with explicit solvent of charge perturbations in biomolecules was slow in the early 1990s because of the widespread use of truncated Coulomb potentials in these simulations, among other factors. Development of the sophisticated technology described in this review to handle the long-range electrostatic interactions has increased the predictive power of these simulations to the point where comparisons between explicit and continuum solvent models can reveal differences that have their true physical origin in the inherent molecularity of the surrounding medium.

  2. Marijuana Revisited.

    ERIC Educational Resources Information Center

    Archer, James, Jr.; Lopata, Ann

    1979-01-01

    This review examines recent research on psychological effects of marijuana. The article contains material on potency, research problems, use patterns in the United States, and expectancy, as well as a review of research on acute effects, including psychosis, toxic delirium, acute anxiety, and brain damage. (Author)

  3. A note on the kinetics of enzyme action: a decomposition that highlights thermodynamic effects.

    PubMed

    Noor, Elad; Flamholz, Avi; Liebermeister, Wolfram; Bar-Even, Arren; Milo, Ron

    2013-09-02

    Michaelis and Menten's mechanism for enzymatic catalysis is remarkable both in its simplicity and its wide applicability. The extension for reversible processes, as done by Haldane, makes it even more relevant as most enzymes catalyze reactions that are reversible in nature and carry in vivo flux in both directions. Here, we decompose the reversible Michaelis-Menten equation into three terms, each with a clear physical meaning: catalytic capacity, substrate saturation and thermodynamic driving force. This decomposition facilitates a better understanding of enzyme kinetics and highlights the relationship between thermodynamics and kinetics, a relationship which is often neglected. We further demonstrate how our separable rate law can be understood from different points of view, shedding light on factors shaping enzyme catalysis.

  4. Amino Acid Specific Effects on RNA Tertiary Interactions: Single-Molecule Kinetic and Thermodynamic Studies.

    PubMed

    Sengupta, Abhigyan; Sung, Hsuan-Lei; Nesbitt, David J

    2016-10-10

    In light of the current models for an early RNA-based universe, the potential influence of simple amino acids on tertiary folding of ribozymal RNA into biochemically competent structures is speculated to be of significant evolutionary importance. In the present work, the folding-unfolding kinetics of a ubiquitous tertiary interaction motif, the GAAA tetraloop-tetraloop receptor (TL-TLR), is investigated by single-molecule fluorescence resonance energy transfer spectroscopy in the presence of natural amino acids both with (e.g., lysine, arginine) and without (e.g., glycine) protonated side chain residues. By way of control, we also investigate the effects of a special amino acid (e.g., proline) and amino acid mimetic (e.g., betaine) that contain secondary or quaternary amine groups rather than a primary amine group. This combination permits systematic study of amino acid induced (or amino acid like) RNA folding dynamics as a function of side chain complexity, pKa, charge state, and amine group content. Most importantly, each of the naturally occurring amino acids is found to destabilize the TL-TLR tertiary folding equilibrium, the kinetic origin of which is dominated by a decrease in the folding rate constant (kdock), also affected by a strongly amino acid selective increase in the unfolding rate constant (kundock). To further elucidate the underlying thermodynamics, single-molecule equilibrium constants (Keq) for TL-TLR folding have been probed as a function of temperature, which reveal an amino acid dependent decrease in both overall exothermicity (ΔΔH° > 0) and entropic cost (-TΔΔS° < 0) for the overall folding process. Temperature-dependent studies on the folding/unfolding kinetic rate constants reveal analogous amino acid specific changes in both enthalpy (ΔΔH(⧧)) and entropy (ΔΔS(⧧)) for accessing the transition state barrier. The maximum destabilization of the TL-TLR tertiary interaction is observed for arginine, which is consistent with early

  5. Structural effects of soft nanoparticulate ligands on trace metal complexation thermodynamics.

    PubMed

    Rotureau, Elise; Waldvogel, Yves; Pinheiro, José P; Farinha, José Paulo S; Bihannic, Isabelle; Présent, Romain M; Duval, Jérôme F L

    2016-11-23

    Metal binding to natural soft colloids is difficult to address due to the inherent heterogeneity of their reactive polyelectrolytic volume and the modifications of their shell structure following changes in e.g. solution pH, salinity or temperature. In this work, we investigate the impacts of temperature- and salinity-mediated modifications of the shell structure of polymeric ligand nanoparticles on the thermodynamics of divalent metal ions Cd(ii)-complexation. The adopted particles consist of a glassy core decorated by a fine-tunable poly(N-isopropylacrylamide) anionic corona. According to synthesis, the charges originating from the metal binding carboxylic moieties supported by the corona chains are located preferentially either in the vicinity of the core or at the outer shell periphery (p(MA-N) and p(N-AA) particles, respectively). Stability constants (KML) of cadmium-nanoparticle complexes are measured under different temperature and salinity conditions using electroanalytical techniques. The obtained KML is clearly impacted by the location of the carboxylic functional groups within the shell as p(MA-N) leads to stronger nanoparticulate Cd complexes than p(N-AA). The dependence of KML on solution salinity for p(N-AA) is shown to be consistent with a binding of Cd to peripheral carboxylic groups driven by Coulombic interactions (Eigen-Fuoss mechanism for ions-pairing) or with particle electrostatic features operating at the edge of the shell Donnan volume. For p(MA-N) particulate ligands, a scenario where metal binding occurs within the intraparticulate Donnan phase correctly reproduces the experimental findings. Careful analysis of electroanalytical data further evidences that complexation of metal ions by core-shell particles significantly differ according to the location and distribution of the metal-binding sites throughout the reactive shell. This complexation heterogeneity is basically enhanced with increasing temperature i.e. upon significant increase of

  6. Recent developments in QCD thermodynamics and collective excitations from hard-thermal-loop effective theory

    NASA Astrophysics Data System (ADS)

    Su, Nan

    2017-03-01

    I summarize recent developments in the hard-thermal-loop approach to QCD. I first discuss a finite-temperature and -density calculation of QCD thermodynamics at NNLO from the hard-thermal-loop perturbation theory. I then discuss a generalization of the hard-thermal-loop framework to the magnetic scale g2T, from which a novel non-Abelian massless mode is uncovered.

  7. Thermodynamics of the hydrophobic effect. III. Condensation and aggregation of alkanes, alcohols, and alkylamines.

    PubMed

    Matulis, D

    2001-10-18

    Knowledge of the energetics of the low solubility of non-polar compounds in water is critical for the understanding of such phenomena as protein folding and biomembrane formation. Solubility in water can be considered as one leg of the three-part thermodynamic cycle - vaporization from the pure liquid, hydration of the vapor in aqueous solution, and aggregation of the substance back into initial pure form as an immiscible phase. Previous studies on the model compounds n-alkanes, 1-alcohols, and 1-aminoalkanes have noted that the thermodynamic parameters (Gibbs free energy, DeltaG; enthalpy, DeltaH; entropy, DeltaS; and heat capacity, DeltaC(p)) associated with these three processes are generally linear functions of the number of carbons in the alkyl chains. Here we assess the accuracy and limitations of the assumption of additivity of CH(2) group contributions to the thermodynamic parameters for vaporization, hydration, and aggregation. Processes of condensation from pure gas to liquid and aqueous solution to aggregate are compared. Hydroxy, amino, and methyl headgroup contributions are estimated, liquid and solid aggregates are distinguished. Most data in the literature were obtained for compounds with short aliphatic hydrocarbon tails. Here we emphasize long aliphatic chain behavior and include our recent experimental data on long chain alkylamine aggregation in aqueous solution obtained by titration calorimetry and van't Hoff analysis. Contrary to what is observed for short compounds, long aliphatic compound aggregation has a large exothermic enthalpy and negative entropy.

  8. Major Effects in the Thermodynamics of Detonation Products: Phase Segregation versus Ionic Dissociation

    SciTech Connect

    Bastea, S; Fried, L E

    2010-03-09

    Water (H{sub 2}O) and nitrogen (N{sub 2}) are major detonation products of high explosives and it has long been conjectured that they may phase segregate at high enough temperatures and pressures to influence detonation properties of common explosives. We analyze the phase diagram of H{sub 2}O-N{sub 2} mixtures using a thermodynamic theory for polar-nonpolar mixtures and find that phase segregation is unlikely to occur above approximately 1600K. Therefore, H{sub 2}O-N{sub 2} immiscibility is not likely to be relevant for detonation predictions. We propose instead that the high pressure ionic dissociation of water plays an important role in detonation, and model it using a new ionic thermodynamics. We employ this model in chemical equilibrium calculations of standard high explosives, e.g. PETN, HMX and RDX, and find that it performs very well under a wide range of conditions. Thus, although it may require further development, it is likely that explicitly ionic thermodynamics will become a standard tool for explosives modeling.

  9. Examining the effects of computational tools on students' understanding of thermodynamics of material concepts and representations

    NASA Astrophysics Data System (ADS)

    Ogunwuyi, Oluwatosin

    Technology is becoming a more critical agent for supporting learning as well as research in science and engineering. In particular, technology-based tools in the form of simulations and virtual environments support learning using mathematical models and computational methods. The purpose of this research is to: (a) measure the value added in conveying Thermodynamics of materials concepts with a blended learning environment using computational simulation tools with lectures; and (b) characterize students' use of representational forms to convey their conceptual understanding of core concepts within a learning environment that blended Gibbs computational resource and traditional lectures. A mix-method approach was implemented that included the use of statistical analysis to compare student test performance as a result of interacting with Gibbs tool and the use of Grounded Theory inductive analysis to explore students' use of representational forms to express their understanding of thermodynamics of material concepts. Results for the quantitative study revealed positive gains in students' conceptual understanding before and after interacting with Gibbs tool for the majority of the concepts tested. In addition, insight gained from the qualitative analysis helped provide understanding about how students utilized representational forms in communicating their understanding of thermodynamics of material concepts. Knowledge of how novice students construct meaning in this context will provide insight for engineering education instructors and researchers in understanding students' learning processes in the context of educational environments that integrate expert simulation tools as part of their instructional resources for foundational domain knowledge.

  10. Viscoplasticity: A thermodynamic formulation

    NASA Technical Reports Server (NTRS)

    Freed, A. D.; Chaboche, J. L.

    1989-01-01

    A thermodynamic foundation using the concept of internal state variables is given for a general theory of viscoplasticity, as it applies to initially isotropic materials. Three fundamental internal state variables are admitted. They are: a tensor valued back stress for kinematic effects, and the scalar valued drag and yield strengths for isotropic effects. All three are considered to phenomenologically evolve according to competitive processes between strain hardening, strain induced dynamic recovery, and time induced static recovery. Within this phenomenological framework, a thermodynamically admissible set of evolution equations is put forth. This theory allows each of the three fundamental internal variables to be composed as a sum of independently evolving constituents.

  11. Factor defining the effects of glycine betaine on the thermodynamic stability and internal dynamics of horse cytochrome C.

    PubMed

    Jain, Rishu; Sharma, Deepak; Kumar, Sandeep; Kumar, Rajesh

    2014-08-19

    A compatible osmolyte such as glycine betaine (GB) and low concentrations of a denaturant constrain the internal dynamics of natively folded carbonmonoxycytochrome c (NCO) at pH 7.0. GB and subdenaturing concentrations of guanidine hydrochloride (GdnHCl) or urea have a cumulative effect on the constrained dynamics of NCO. At higher denaturant concentrations, large-scale unfolding fluctuations dominate the dynamics and inclusion of GB opposes the structural fluctuations that cause unfolding of the protein. These deductions are made from kinetic and thermodynamic parameters measured for the CO dissociation reaction of NCO at varying concentrations of denaturant in the absence and presence of 1.0 M GB. Intermolecular docking between horse ferrocytochrome c and a denaturant or GB reveals that the denaturant-mediated constrained dynamics of the protein is due to polyfunctional interactions between the denaturant and different groups of protein while the GB-mediated restricted dynamics of the protein arises from both the direct interactions of GB with different side chains of Lys or Arg residues of the protein and indirect interactions of GB with the protein surface. Thermodynamic analysis of the thermal and GdnHCl-induced unfolding curves of ferrocytochrome c measured in the absence and presence of 1.0 M GB at pH 7.0 indicates that GB increases the thermodynamic stability of ferrocytochrome c at neutral pH. Analysis of thermal and urea-induced unfolding curves of ferricytochrome c measured at different GdnHCl concentrations in the absence and presence of 0.5-1.0 M GB at pH 7.0 and 3.8 suggests that GB counteracts the destabilizing effect of the denaturant at pH 7.0 but exhibits an additive effect on the destabilizing effect of the denaturant at pH 3.8.

  12. The Pill Not Taken: Revisiting Physical Education Teacher Effectiveness in a Public Health Context

    ERIC Educational Resources Information Center

    McKenzie, Thomas L.; Lounsbery, Monica A. F.

    2014-01-01

    In "Physical Education Teacher Effectiveness in a Public Health Context," we took a broad view of physical education (PE) teacher effectiveness that included public health need and support for PE. Public health officials have been consistent and fervent in their support of PE, and for more than two decades, they have called on schools to…

  13. The Demise of Short-Term Memory Revisited: Empirical and Computational Investigations of Recency Effects

    ERIC Educational Resources Information Center

    Davelaar,Eddy J.; Goshen-Gottstein, Yonatan; Ashkenazi, Amir; Haarmann, Henk J.; Usher, Marius

    2005-01-01

    In the single-store model of memory, the enhanced recall for the last items in a free-recall task (i.e., the recency effect) is understood to reflect a general property of memory rather than a separate short-term store. This interpretation is supported by the finding of a long-term recency effect under conditions that eliminate the contribution…

  14. Calcium revisited, part III: effect of dietary calcium on BMD and fracture risk

    PubMed Central

    Burckhardt, Peter

    2015-01-01

    Food can be an excellent source of calcium. Dietary calcium is in general as well absorbed as calcium supplements, and exerts the same effects on bone. The main sources are dairy products, but also some vegetables and fruits contain considerable amounts of calcium. Mineral water can serve as a supplement. Cross-sectional, longitudinal and some interventional trials have shown positive effects on bone metabolism, bone density and bone loss. But the effect on fracture incidence is less certain, and that of milk, the most studied dairy product, still unproven. PMID:26331006

  15. Nitroprusside Revisited

    PubMed Central

    Mani, M. K.

    1971-01-01

    Sodium nitroprusside is a readily available, powerful hypotensive agent. It was administered intravenously in four cases when all other available hypotensive agents had failed, and blood pressure was controlled promptly and with no side effects. This is a valuable drug and deserves wider use. PMID:5566620

  16. Turbulence effects on warm-rain formation in precipitating shallow convection revisited

    NASA Astrophysics Data System (ADS)

    Seifert, Axel; Onishi, Ryo

    2016-09-01

    Two different collection kernels which include turbulence effects on the collision rate of liquid droplets are used as a basis to develop a parameterization of the warm-rain processes autoconversion, accretion, and self-collection. The new parameterization is tested and validated with the help of a 1-D bin microphysics model. Large-eddy simulations of the rain formation in shallow cumulus clouds confirm previous results that turbulence effects can significantly enhance the development of rainwater in clouds and the occurrence and amount of surface precipitation. The detailed behavior differs significantly for the two turbulence models, revealing a considerable uncertainty in our understanding of such effects. In addition, the large-eddy simulations show a pronounced sensitivity to grid resolution, which suggests that besides the effect of sub-grid small-scale isotropic turbulence which is parameterized as part of the collection kernel also the larger turbulent eddies play an important role for the formation of rain in shallow clouds.

  17. What Light through Yonder Window Breaks?--The Greenhouse Effect Revisited.

    ERIC Educational Resources Information Center

    Bohren, Craig F.

    1992-01-01

    Presents three experiments exploring aspects of the greenhouse effect. Topics and discussion includes radiation in energy transfer, emissivity and absorptivity, the irrelevance of reflectivity, a digression on insulators and convection, climate change, and radiative energy balance. (MCO)

  18. Recognizing off-target drug effects in the gut and brain: revisiting isotretinoin and depression.

    PubMed

    Kollipara, R; Reisz, C

    2016-04-01

    Clinicians often face complex decisions regarding off-target drug effects, both in diagnosis and treatment. A key component in the formulation of the correct diagnosis is the temporal relationship between drug introduction and adverse effect. The sentinel injury may target the gut and brain. The description of the complaint may vary among providers. Modeling Information visualization for clinicians in real time will require the integration of time-stamped data with organ-specific complaints.

  19. Nonthermal microwave effects revisited: on the importance of internal temperature monitoring and agitation in microwave chemistry.

    PubMed

    Herrero, M Antonia; Kremsner, Jennifer M; Kappe, C Oliver

    2008-01-04

    The concept of nonthermal microwave effects has received considerable attention in recent years and is the subject of intense debate in the scientific community. Nonthermal microwave effects have been postulated to result from a direct stabilizing interaction of the electric field with specific (polar) molecules in the reaction medium that is not related to a macroscopic temperature effect. In order to probe the existence of nonthermal microwave effects, four synthetic transformations (Diels-Alder cycloaddition, alkylation of triphenylphosphine and 1,2,4-triazole, direct amide bond formation) were reevaluated under both microwave dielectric heating and conventional thermal heating. In all four cases, previous studies have claimed the existence of nonthermal microwave effects in these reactions. Experimentally, significant differences in conversion and/or product distribution comparing the conventionally and microwave-heated experiments performed at the same measured reaction temperature were found. The current reevaluation of these reactions was performed in a dedicated reactor setup that allowed accurate internal reaction temperature measurements using a multiple fiber-optic probe system. Using this technology, the importance of efficient stirring and internal temperature measurement in microwave-heated reactions was made evident. Inefficient agitation leads to temperature gradients within the reaction mixture due to field inhomogeneities in the microwave cavity. Using external infrared temperature sensors in some cases results in significant inaccuracies in the temperature measurement. Applying the fiber-optic probe temperature monitoring device, a critical reevaluation of all four reactions has provided no evidence for the existence of nonthermal microwave effects. Ensuring efficient agitation of the reaction mixture via magnetic stirring, no significant differences in terms of conversion and selectivity between experiments performed under microwave or oil bath

  20. Cats protecting birds revisited.

    PubMed

    Fan, Meng; Kuang, Yang; Feng, Zhilan

    2005-09-01

    In this paper, we revisit the dynamical interaction among prey (bird), mesopredator (rat), and superpredator (cat) discussed in [Courchamp, F., Langlais, M., Sugihara, G., 1999. Cats protecting birds: modelling the mesopredator release effect. Journal of Animal Ecology 68, 282-292]. First, we develop a prey-mesopredator-superpredator (i.e., bird-rat-cat, briefly, BRC) model, where the predator's functional responses are derived based on the classical Holling's time budget arguments. Our BRC model overcomes several model construction problems in Courchamp et al. (1999), and admits richer, reasonable and realistic dynamics. We explore the possible control strategies to save or restore the bird by controlling or eliminating the rat or the cat when the bird is endangered. We establish the existence of two types of mesopredator release phenomena: severe mesopredator release, where once superpredators are suppressed, a burst of mesopredators follows which leads their shared prey to extinction; and mild mesopredator release, where the mesopredator release could assert more negative impact on the endemic prey but does not lead the endemic prey to extinction. A sharp sufficient criterion is established for the occurrence of severe mesopredator release. We also show that, in a prey-mesopredator-superpredator trophic food web, eradication of introduced superpredators such as feral domestic cats in the BRC model, is not always the best solution to protect endemic insular prey. The presence of a superpredator may have a beneficial effect in such systems.

  1. Iodine revisited.

    PubMed

    Cooper, Rose A

    2007-06-01

    Iodine is an antiseptic that has been used in wound care for more than 150 years. Traditional formulations of iodine had serious limitations that were reduced in later products. Much has been written about iodine and opinions on its clinical efficacy are divided. There have been reviews of the chemical properties of iodine, its antimicrobial activity, human physiology, cytotoxicity and its clinical effectiveness, but few have addressed all these aspects. With the recent development of iodine-containing wound care products and the continued publication of laboratory and clinical studies, it seems timely to reassess the evidence relating to the effectiveness of iodine for treating wounds. This literature review attempts to provide an appropriate chemical and physiological background of the characteristics of iodine in order to provide a sound basis for understanding the available microbiological and clinical data. It will show that understanding the factors that contribute to the activity and potential cytotoxicity of iodine are important in evaluating the clinical evidence. Although definitive studies are needed, the sustained delivery of low doses of free iodine offers the potential to inhibit a broad range of microbial species without selecting for resistant strains or inducing cytotoxic effects.

  2. The Bosma effect revisited. I. HI and stellar disc scaling models

    NASA Astrophysics Data System (ADS)

    Hessman, F. V.; Ziebart, M.

    2011-08-01

    Context. The observed proportionality between the centripetal contribution of the dynamically insignificant HI gas in the discs of spiral galaxies and the dominant contribution of dark matter (DM) - the "Bosma effect" - has been repeatedly mentioned in the literature but largely ignored. Since this phenomenology, if statistically significant, tells us something about the relationship between the visible baryonic and invisible DM, it is important to re-examine the reality of this effect using formal tests and more modern data. Aims: We have re-examined the evidence for the Bosma effect, either by scaling the contribution of the HI gas alone or by using both the observed stellar disc and HI gas as proxies. Methods: We have calculated Bosma effect models for 17 galaxies in The HI Nearby Galaxy Survey data set. The results are compared with two models for exotic cold DM: internally consistent cosmological Navarro-Frenk-White (NFW) models with constrained compactness parameters, and "universal rotation curve" (URC) models using fully unconstrained Burkert density profiles. Results: Fits to spiral galaxy rotation curves computed using just HI scaling are inadequate, despite the clear proportionality seen in the outer discs. The poor performance is obviously related to the prominent decrease in the HI surface density in regions of high stellar surface density, where HI has been converted into molecules and stars. The Bosma models that partially correct for this physical effect using the stellar discs as additional proxies are statistically nearly as good as the URC models and clearly better than the NFW ones. Conclusions: We confirm the correlation between the centripetal effects of DM and that of the interstellar medium of spiral galaxies. The efficacy of "maximal disc" models is explained as the natural consequence of "classic" Bosma models which include the stellar disc as a proxy in regions of reduced atomic gas. The perception that the Bosma effect could be due to

  3. Prediction of cavitation performance and choking flow limit of inducers for cold water and for fluids with thermodynamic effect

    NASA Astrophysics Data System (ADS)

    Sauvage-Boutar, E.; Desclaux, J.

    1990-07-01

    Two methods of prediction of partial cavitation in inducers of rocket engine turbopumps have been developed. The first one is an analytical method previously developed to predict minimum NPSH (inlet total head minus vapor pressure) and the choking flow limit which was modified to include the computation of blade and boundary layer blockage. The second one is a method based on the work of Moore and Ruggeri (1969). This method takes into account thermodynamic effect for the prediction of the cavitation parameter Ki. For the choking flow limit, the first method can be extended to cryogenic fluids. Comparisons with available experimental data obtained with VULCAIN inducer pumping water and liquid hydrogen are presented.

  4. Perceptual effects of linguistic category priming: the Stapel and Semin (2007) paradigm revisited in twelve experiments.

    PubMed

    IJzerman, Hans; Regenberg, Nina F E; Saddlemyer, Justin; Koole, Sander L

    2015-05-01

    Linguistic category priming is a novel paradigm to examine automatic influences of language on cognition (Semin, 2008). An initial article reported that priming abstract linguistic categories (adjectives) led to more global perceptual processing, whereas priming concrete linguistic categories (verbs) led to more local perceptual processing (Stapel & Semin, 2007). However, this report was compromised by data fabrication by the first author, so that it remains unclear whether or not linguistic category priming influences perceptual processing. To fill this gap in the literature, the present article reports 12 studies among Dutch and US samples examining the perceptual effects of linguistic category priming. The results yielded no evidence of linguistic category priming effects. These findings are discussed in relation to other research showing cultural variations in linguistic category priming effects (IJzerman, Saddlemyer, & Koole, 2014). The authors conclude by highlighting the importance of conducting and publishing replication research for achieving scientific progress.

  5. New evidence of the effects of education on health in the US: compulsory schooling laws revisited.

    PubMed

    Fletcher, Jason M

    2015-02-01

    Estimating the effects of education on health and mortality has been the subject of intense debate and competing findings and summaries. The original Lleras-Muney (2005) methods utilizing state compulsory schooling laws as instrumental variables for completed education and US data to establish effects of education on mortality have been extended to several countries, with mixed and often null findings. However, additional US studies have lagged behind due to small samples and/or lack of mortality information in many available datasets. This paper uses a large, novel survey from the AARP on several hundred thousand respondents to present new evidence of the effects of education on a variety of health outcomes. Results suggest that education may have a role in improving several dimensions of health, such as self reports, cardiovascular outcomes, and weight outcomes. Other results appear underpowered, suggesting that further use of this methodology may require even larger, and potentially unattainable, sample sizes in the US.

  6. Revisiting the picture-superiority effect in symbolic comparisons: do pictures provide privileged access?

    PubMed

    Amrhein, Paul C; McDaniel, Mark A; Waddill, Paula

    2002-09-01

    In 4 experiments, symbolic comparisons were investigated to test semantic-memory retrieval accounts espousing processing advantages for picture over word stimuli. In Experiment 1, participants judged pairs of animal names or pictures by responding to questions probing concrete or abstract attributes (texture or size, ferocity or intelligence). Per pair, attributes were salient or nonsalient concerning their prerated relevance to animals being compared. Distance (near or far) between attribute magnitudes was also varied. Pictures did not significantly speed responding relative to words across all other variables. Advantages were found forfar attribute magnitudes (i.e., the distance effect) and salient attributes. The distance effect was much less for salient than nonsalient concrete-attribute comparisons. These results were consistently found in additional experiments with increased statistical power to detect modality effects. Our findings argue against dual-coding and some common-code accounts of conceptual attribute processing, urging reexamination of the assumption that pictures confer privileged access to long-term knowledge.

  7. The orexigenic effect of orexin-A revisited: dependence of an intact growth hormone axis.

    PubMed

    Álvarez-Crespo, Mayte; Martínez-Sánchez, Noelia; Ruíz-Pino, Francisco; Garcia-Lavandeira, Montserrat; Alvarez, Clara V; Tena-Sempere, Manuel; Nogueiras, Rubén; Diéguez, Carlos; López, Miguel

    2013-10-01

    Fifteen years ago orexins were identified as central regulators of energy homeostasis. Since then, that concept has evolved considerably and orexins are currently considered, besides orexigenic neuropeptides, key modulators of sleep-wake cycle and neuroendocrine function. Little is known, however, about the effect of the neuroendocrine milieu on orexins' effects on energy balance. We therefore investigated whether hypothalamic-pituitary axes have a role in the central orexigenic action of orexin A (OX-A) by centrally injecting hypophysectomized, adrenalectomized, gonadectomized (male and female), hypothyroid, and GH-deficient dwarf rats with OX-A. Our data showed that the orexigenic effect of OX-A is fully maintained in adrenalectomized and gonadectomized (females and males) rats, slightly reduced in hypothyroid rats, and totally abolished in hypophysectomized and dwarf rats when compared with their respective vehicle-treated controls. Of note, loss of the OX-A effect on feeding was associated with a blunted OX-A-induced increase in the expression of either neuropeptide Y or its putative regulator, the transcription factor cAMP response-element binding protein, as well as its phosphorylated form, in the arcuate nucleus of the hypothalamus of hypophysectomized and dwarf rats. Overall, this evidence suggests that the orexigenic action of OX-A depends on an intact GH axis and that this neuroendocrine feedback loop may be of interest in the understanding of orexins action on energy balance and GH deficiency.

  8. Revisiting the Complementarity between Education and Training--The Role of Job Tasks and Firm Effects

    ERIC Educational Resources Information Center

    Görlitz, Katja; Tamm, Marcus

    2016-01-01

    This paper addresses the question to what extent the strong positive correlation between education and training can be attributed to differences in individual-, job- and firm-specific characteristics. The novelty of this paper is to analyze previously unconsidered characteristics, in particular, job tasks and firm-fixed effects. The results show…

  9. The Labial-Coronal Effect Revisited: Japanese Adults Say Pata, but Hear Tapa

    ERIC Educational Resources Information Center

    Tsuji, Sho; Gomez, Nayeli Gonzalez; Medina, Victoria; Nazzi, Thierry; Mazuka, Reiko

    2012-01-01

    The labial-coronal effect has originally been described as a bias to initiate a word with a labial consonant-vowel-coronal consonant (LC) sequence. This bias has been explained with constraints on the human speech production system, and its perceptual correlates have motivated the suggestion of a perception-production link. However, previous…

  10. The Reciprocal Effects Model Revisited: Extending Its Reach to Gifted Students Attending Academically Selective Schools

    ERIC Educational Resources Information Center

    Seaton, Marjorie; Marsh, Herbert W.; Parker, Philip D.; Craven, Rhonda G.; Yeung, Alexander S.

    2015-01-01

    The reciprocal effects model (REM) predicts a reciprocal relation between academic self-concept and academic achievement, whereby prior academic self-concept is associated with future gains in achievement, and prior achievement is related to subsequent academic self-concept. Although research in this area has been extensive, there has been a…

  11. The Misinformation Effect Revisited: Interactions between Spontaneous Memory Processes and Misleading Suggestions

    ERIC Educational Resources Information Center

    Pansky, Ainat; Tenenboim, Einat; Bar, Sarah Kate

    2011-01-01

    Recent findings indicate that retained information tends to converge at the basic level (BL). The aim of the present study was to apply these findings to the investigation of misinformation phenomena. In three experiments, we examined the extent to which the contaminating effects of misinformation are influenced by its consistency with the…

  12. The Efficiency of a Group-Specific Mandated Benefit Revisited: The Effect of Infertility Mandates

    ERIC Educational Resources Information Center

    Lahey, Joanna N.

    2012-01-01

    This paper examines the labor market effects of state health insurance mandates that increase the cost of employing a demographically identifiable group. State mandates requiring that health insurance plans cover infertility treatment raise the relative cost of insuring older women of child-bearing age. Empirically, wages in this group are…

  13. Revisiting Parental Monitoring: Evidence that Parental Solicitation Can Be Effective when Needed Most

    ERIC Educational Resources Information Center

    Laird, Robert D.; Marrero, Matthew D.; Sentse, Miranda

    2010-01-01

    Studies using valid measures of monitoring activities have not found the anticipated main effects linking greater monitoring activity with fewer behavioral problems. This study focused on two contexts in which monitoring activities may be particularly influential. Early adolescents (n = 218, M age = 11.5 years, 51% female, 49% European American,…

  14. Revisiting the Seductive Details Effect in Multimedia Learning: Context-Dependency of Seductive Details

    ERIC Educational Resources Information Center

    Ozdemir, Devrim; Doolittle, Peter

    2015-01-01

    The purpose of this study was to investigate the effects of context-dependency of seductive details on recall and transfer in multimedia learning environments. Seductive details were interesting yet irrelevant sentences in the instructional text. Two experiments were conducted. The purpose of Experiment 1 was to identify context-dependent and…

  15. Revisiting Gordon's Teacher Effectiveness Training: An Intervention Study on Teachers' Social and Emotional Learning

    ERIC Educational Resources Information Center

    Talvio, Markus; Lonka, Kirsti; Komulainen, Erkki; Kuusela, Marjo; Lintunen, Taru

    2013-01-01

    Introduction: This study explored the development of teachers' social and emotional learning (SEL) skills by using "Teacher Effectiveness Training (TET)" (Gordon Training International) as an intervention with two groups of teachers. Further Gordon's model was approached from the perspective of modern educational psychology. The effects…

  16. Role Stress Revisited: Job Structuring Antecedents, Work Outcomes, and Moderating Effects of Locus of Control

    ERIC Educational Resources Information Center

    Conley, Sharon; You, Sukkyung

    2014-01-01

    A previous study examined role stress in relation to work outcomes; in this study, we added job structuring antecedents to a model of role stress and examined the moderating effects of locus of control. Structural equation modeling was used to assess the plausibility of our conceptual model, which specified hypothesized linkages among teachers'…

  17. Revisiting Fixed- and Random-Effects Models: Some Considerations for Policy-Relevant Education Research

    ERIC Educational Resources Information Center

    Clarke, Paul; Crawford, Claire; Steele, Fiona; Vignoles, Anna

    2015-01-01

    The use of fixed (FE) and random effects (RE) in two-level hierarchical linear regression is discussed in the context of education research. We compare the robustness of FE models with the modelling flexibility and potential efficiency of those from RE models. We argue that the two should be seen as complementary approaches. We then compare both…

  18. Remote Sensing the Vertical Profile of Cloud Droplet Effective Radius, Thermodynamic Phase, and Temperature

    NASA Technical Reports Server (NTRS)

    Martins, J. V.; Marshak, A.; Remer, L. A.; Rosenfeld, D.; Kaufman, Y. J.; Fernandez-Borda, R.; Koren, I.; Correia, A. L.; Zubko, V.; Artaxo, P.

    2011-01-01

    Cloud-aerosol interaction is a key issue in the climate system, affecting the water cycle, the weather, and the total energy balance including the spatial and temporal distribution of latent heat release. Information on the vertical distribution of cloud droplet microphysics and thermodynamic phase as a function of temperature or height, can be correlated with details of the aerosol field to provide insight on how these particles are affecting cloud properties and their consequences to cloud lifetime, precipitation, water cycle, and general energy balance. Unfortunately, today's experimental methods still lack the observational tools that can characterize the true evolution of the cloud microphysical, spatial and temporal structure in the cloud droplet scale, and then link these characteristics to environmental factors and properties of the cloud condensation nuclei. Here we propose and demonstrate a new experimental approach (the cloud scanner instrument) that provides the microphysical information missed in current experiments and remote sensing options. Cloud scanner measurements can be performed from aircraft, ground, or satellite by scanning the side of the clouds from the base to the top, providing us with the unique opportunity of obtaining snapshots of the cloud droplet microphysical and thermodynamic states as a function of height and brightness temperature in clouds at several development stages. The brightness temperature profile of the cloud side can be directly associated with the thermodynamic phase of the droplets to provide information on the glaciation temperature as a function of different ambient conditions, aerosol concentration, and type. An aircraft prototype of the cloud scanner was built and flew in a field campaign in Brazil.

  19. Anion effects on kinetics and thermodynamics of CO2 absorption in ionic liquids.

    PubMed

    Gonzalez-Miquel, Maria; Bedia, Jorge; Abrusci, Concepcion; Palomar, Jose; Rodriguez, Francisco

    2013-03-28

    A thermogravimetric technique based on a magnetic suspension balance operating in dynamic mode was used to study the thermodynamics (in terms of solubility and Henry's law constants) and kinetics (i.e., diffusion coefficients) of CO2 in the ionic liquids [bmim][PF6], [bmim][NTf2], and [bmim][FAP] at temperatures of 298.15, 308.15, and 323.15 K and pressures up to 20 bar. The experimental technique employed was shown to be a fast, accurate, and low-solvent-consuming method to evaluate the suitability of the ionic liquids (ILs) to be used as CO2 absorbents. Thermodynamic results confirmed that the solubility of CO2 in the ILs followed the order [bmim][FAP] > [bmim][NTf2] > [bmim][PF6], increasing with decreasing temperatures and increasing pressures. Kinetic data showed that the diffusion coefficients of CO2 in the ILs followed a different order, [bmim][NTf2] > [bmim][FAP] > [bmim][PF6], increasing with increasing temperatures and pressures. These results evidenced the different influence of the IL structure and operating conditions on the solubility and absorption rate of CO2, illustrating the importance of considering both thermodynamic and kinetic aspects to select adequate ILs for CO2 absorption. On the other hand, the empirical Wilke-Chang correlation was successfully applied to estimate the diffusion coefficients of the systems, with results indicating the suitability of this approach to foresee the kinetic performance of ILs to absorb CO2. The research methodology proposed herein might be helpful in the selection of efficient absorption solvents based on ILs for postcombustion CO2 capture.

  20. Sulfur revisited.

    PubMed

    Lin, A N; Reimer, R J; Carter, D M

    1988-03-01

    Sulfur is a time-honored therapeutic agent useful in a variety of dermatologic disorders. Its keratolytic action is due to formation of hydrogen sulfide through a reaction that depends upon direct interaction between sulfur particles and keratinocytes. The smaller the particle size, the greater the degree of such interaction and the greater the therapeutic efficacy. When applied topically, sulfur induces various histologic changes, including hyperkeratosis, acanthosis, and dilatation of dermal vasculature. One study showed that sulfur was comedogenic when applied onto human and rabbit skin, findings that were not reproduced in other studies. About 1% of topically applied sulfur is systemically absorbed. Adverse effects from topically applied sulfur are uncommon and are mainly limited to the skin. In infants, however, fatal outcome after extensive application has been reported.

  1. Penicillamine revisited: historic overview and review of the clinical uses and cutaneous adverse effects.

    PubMed

    Ishak, Rim; Abbas, Ossama

    2013-06-01

    Penicillamine is a well-known heavy metal chelator, classically used in the treatment of Wilson disease, rheumatoid arthritis, and cystinuria. From a dermatologic standpoint, penicillamine was found to be useful in the treatment of systemic sclerosis. The successful therapeutic uses of penicillamine have been hindered by its numerous adverse effects, both cutaneous and extra-cutaneous. It is a unique drug since it provokes a diversity of dermatologic manifestations that include (1) acute hypersensitivity reactions, (2) dermopathies characterized by elastic fiber abnormalities including elastosis perforans serpiginosa and pseudo-pseudoxanthoma elasticum, (3) autoimmune disorders such as pemphigus and penicillamine-induced lupus erythematosus-like syndrome, and (4) miscellaneous dermatoses that result from undefined mechanisms. These cutaneous adverse effects may correlate with the dosage and duration of penicillamine therapy as well as the disease being treated.

  2. Revisiting parental monitoring: evidence that parental solicitation can be effective when needed most.

    PubMed

    Laird, Robert D; Marrero, Matthew D; Sentse, Miranda

    2010-12-01

    Studies using valid measures of monitoring activities have not found the anticipated main effects linking greater monitoring activity with fewer behavioral problems. This study focused on two contexts in which monitoring activities may be particularly influential. Early adolescents (n = 218, M age = 11.5 years, 51% female, 49% European American, 47% African American) reported their unsupervised time, beliefs about the legitimacy of their parents' authority, and their own involvement in antisocial behavior. Mothers and adolescents reported their perceptions of adolescent disclosure and parental solicitation and control. Adolescents' perceptions of greater parental solicitation at age 11 were associated with less antisocial behavior at age 12 (when controlling for age 11 antisocial behavior) among adolescents reporting large amounts of unsupervised time and weak legitimacy beliefs. Perceived parental solicitation may be an effective deterrent of antisocial behavior when adolescents spend a lot of time unsupervised and for adolescents who are likely to challenge the legitimacy of their parents' authority.

  3. The Reverse-Caricature Effect Revisited: Familiarization With Frontal Facial Caricatures Improves Veridical Face Recognition.

    PubMed

    Rodríguez, Jobany; Bortfeld, Heather; Rudomín, Isaac; Hernández, Benjamín; Gutiérrez-Osuna, Ricardo

    2009-07-01

    Prior research suggests that recognition of a person's face can be facilitated by exaggerating the distinctive features of the face during training. We tested if this 'reverse-caricature effect' would be robust to procedural variations that created more difficult learning environments. Specifically, we examined whether the effect would emerge with frontal rather than three-quarter views, after very brief exposure to caricatures during the learning phase and after modest rotations of faces during the recognition phase. Results indicate that, even under these difficult training conditions, people are more accurate at recognizing unaltered faces if they are first familiarized with caricatures of the faces, rather than with the unaltered faces. These findings support the development of new training methods to improve face recognition.

  4. Very Large Array Detection of the 36 GHz Zeeman Effect in DR21W Revisited

    NASA Astrophysics Data System (ADS)

    Momjian, Emmanuel; Sjouwerman, Loránt O.; Fish, Vincent L.

    2012-09-01

    We report on the observation of the 36 GHz methanol maser line in the star-forming region DR21W to accurately measure the Zeeman effect. The Zeeman signature reported by Fish et al. became suspicious after an instrumental effect was discovered in the early days of the commissioning of the Very Large Array Wide-band Digital Architecture correlator. We conclude that the previously reported magnetic field strength of 58 mG (1.7 Hz mG-1/z) is instrumental in nature and thus incorrect. With the improved performance of the array, we now deduce a 3σ limit of -4.7 to +0.4 mG (1.7 Hz mG-1/z) for the line-of-sight component of the magnetic field strength in DR21W.

  5. VERY LARGE ARRAY DETECTION OF THE 36 GHz ZEEMAN EFFECT IN DR21W REVISITED

    SciTech Connect

    Momjian, Emmanuel; Sjouwerman, Lorant O.; Fish, Vincent L.

    2012-09-20

    We report on the observation of the 36 GHz methanol maser line in the star-forming region DR21W to accurately measure the Zeeman effect. The Zeeman signature reported by Fish et al. became suspicious after an instrumental effect was discovered in the early days of the commissioning of the Very Large Array Wide-band Digital Architecture correlator. We conclude that the previously reported magnetic field strength of 58 mG (1.7 Hz mG{sup -1}/z) is instrumental in nature and thus incorrect. With the improved performance of the array, we now deduce a 3{sigma} limit of -4.7 to +0.4 mG (1.7 Hz mG{sup -1}/z) for the line-of-sight component of the magnetic field strength in DR21W.

  6. The labial-coronal effect revisited: Japanese adults say pata, but hear tapa.

    PubMed

    Tsuji, Sho; Gomez, Nayeli Gonzalez; Medina, Victoria; Nazzi, Thierry; Mazuka, Reiko

    2012-12-01

    The labial-coronal effect has originally been described as a bias to initiate a word with a labial consonant-vowel-coronal consonant (LC) sequence. This bias has been explained with constraints on the human speech production system, and its perceptual correlates have motivated the suggestion of a perception-production link. However, previous studies exclusively considered languages in which LC sequences are globally more frequent than their counterpart. The current study examined the LC bias in speakers of Japanese, a language that has been claimed to possess more CL than LC sequences. We first conducted an analysis of Japanese corpora that qualified this claim, and identified a subgroup of consonants (plosives) exhibiting a CL bias. Second, focusing on this subgroup of consonants, we found diverging results for production and perception such that Japanese speakers exhibited an articulatory LC bias, but a perceptual CL bias. The CL perceptual bias, however, was modulated by language of presentation, and was only present for stimuli recorded by a Japanese, but not a French, speaker. A further experiment with native speakers of French showed the opposite effect, with an LC bias for French stimuli only. Overall, we find support for a universal, articulatory motivated LC bias in production, supporting a motor explanation of the LC effect, while perceptual biases are influenced by distributional frequencies of the native language.

  7. The Baldwin effect and genetic assimilation: revisiting two mechanisms of evolutionary change mediated by phenotypic plasticity.

    PubMed

    Crispo, Erika

    2007-11-01

    Two different, but related, evolutionary theories pertaining to phenotypic plasticity were proposed by James Mark Baldwin and Conrad Hal Waddington. Unfortunately, these theories are often confused with one another. Baldwin's notion of organic selection posits that plasticity influences whether an individual will survive in a new environment, thus dictating the course of future evolution. Heritable variations can then be selected upon to direct phenotypic evolution (i.e., "orthoplasy"). The combination of these two processes (organic selection and orthoplasy) is now commonly referred to as the "Baldwin effect." Alternately, Waddington's genetic assimilation is a process whereby an environmentally induced phenotype, or "acquired character," becomes canalized through selection acting upon the developmental system. Genetic accommodation is a modern term used to describe the process of heritable changes that occur in response to a novel induction. Genetic accommodation is a key component of the Baldwin effect, and genetic assimilation is a type of genetic accommodation. I here define both the Baldwin effect and genetic assimilation in terms of genetic accommodation, describe cases in which either should occur in nature, and propose that each could play a role in evolutionary diversification.

  8. Revisiting Wasson's Soma: exploring the effects of preparation on the chemistry of Amanita muscaria.

    PubMed

    Feeney, Kevin

    2010-12-01

    In 1968 R. Gordon Wasson first proposed his groundbreaking theory identifying Soma, the hallucinogenic sacrament of the Vedas, as the Amanita muscaria mushroom. While Wasson's theory has garnered acclaim, it is not without its faults. One omission in Wasson's theory is his failure to explain how pressing and filtering Soma, as described in the Rig Veda, supports his theory of Soma's identity. Several critics have reasoned that such preparation should be unnecessary if equivalent results can be obtained by consuming the raw plant, as is done with other psychoactive mushrooms. In order to address these specific criticisms over 600 anecdotal accounts of Amanita muscaria inebriation were collected and analyzed to determine the impact of preparation on Amanita muscaria's effects. The findings of this study demonstrated that the effects of Amanita muscaria were related to the type of preparation employed, and that its toxic effects were considerably reduced by preparations that paralleled those described for Soma in the Rig Veda. While unlikely to end debate over the identity of Soma, this study's findings help to solidify the foundation of Wasson's theory, and also to demonstrate the importance of preparation in understanding and uncovering the true identity of Soma.

  9. Revisiting age-of-acquisition effects in Spanish visual word recognition: the role of item imageability.

    PubMed

    Wilson, Maximiliano A; Cuetos, Fernando; Davies, Rob; Burani, Cristina

    2013-11-01

    Word age-of-acquisition (AoA) affects reading. The mapping hypothesis predicts AoA effects when input-output mappings are arbitrary. In Spanish, the orthography-to-phonology mappings required for word naming are consistent; therefore, no AoA effects are expected. Nevertheless, AoA effects have been found, motivating the present investigation of how AoA can affect reading in Spanish. Four experiments were run to examine reading with a factorial design manipulating AoA and frequency. In Experiments 1 and 2 (immediate and speeded naming), only word frequency affected word naming. In Experiment 3 (lexical decision), both AoA and frequency affected word recognition. In Experiment 4 (immediate naming with highly imageable items), both frequency and AoA affected naming. The results suggest that highly imageable items induce a larger reliance on semantics in reading aloud. Such reliance causes faster naming of earlier acquired words because the corresponding concepts have richer visual and sensory features acquired mainly through direct sensory experience.

  10. Thermodynamics of Biological Processes

    PubMed Central

    Garcia, Hernan G.; Kondev, Jane; Orme, Nigel; Theriot, Julie A.; Phillips, Rob

    2012-01-01

    There is a long and rich tradition of using ideas from both equilibrium thermodynamics and its microscopic partner theory of equilibrium statistical mechanics. In this chapter, we provide some background on the origins of the seemingly unreasonable effectiveness of ideas from both thermodynamics and statistical mechanics in biology. After making a description of these foundational issues, we turn to a series of case studies primarily focused on binding that are intended to illustrate the broad biological reach of equilibrium thinking in biology. These case studies include ligand-gated ion channels, thermodynamic models of transcription, and recent applications to the problem of bacterial chemotaxis. As part of the description of these case studies, we explore a number of different uses of the famed Monod–Wyman–Changeux (MWC) model as a generic tool for providing a mathematical characterization of two-state systems. These case studies should provide a template for tailoring equilibrium ideas to other problems of biological interest. PMID:21333788

  11. An analysis of quantum effects on the thermodynamic properties of cryogenic hydrogen using the path integral method

    SciTech Connect

    Nagashima, H.; Tsuda, S.; Tsuboi, N.; Koshi, M.; Hayashi, K. A.; Tokumasu, T.

    2014-04-07

    In this paper, we describe the analysis of the thermodynamic properties of cryogenic hydrogen using classical molecular dynamics (MD) and path integral MD (PIMD) method to understand the effects of the quantum nature of hydrogen molecules. We performed constant NVE MD simulations across a wide density–temperature region to establish an equation of state (EOS). Moreover, the quantum effect on the difference of molecular mechanism of pressure–volume–temperature relationship was addressed. The EOS was derived based on the classical mechanism idea only using the MD simulation results. Simulation results were compared with each MD method and experimental data. As a result, it was confirmed that although the EOS on the basis of classical MD cannot reproduce the experimental data of saturation property of hydrogen in the high-density region, the EOS on the basis of PIMD well reproduces those thermodynamic properties of hydrogen. Moreover, it was clarified that taking quantum effects into account makes the repulsion force larger and the potential well shallower. Because of this mechanism, the intermolecular interaction of hydrogen molecules diminishes and the virial pressure increases.

  12. The effect of particle size on the morphology and thermodynamics of diblock copolymer/tethered-particle membranes

    SciTech Connect

    Zhang, Bo; Edwards, Brian J.

    2015-06-07

    A combination of self-consistent field theory and density functional theory was used to examine the effect of particle size on the stable, 3-dimensional equilibrium morphologies formed by diblock copolymers with a tethered nanoparticle attached either between the two blocks or at the end of one of the blocks. Particle size was varied between one and four tenths of the radius of gyration of the diblock polymer chain for neutral particles as well as those either favoring or disfavoring segments of the copolymer blocks. Phase diagrams were constructed and analyzed in terms of thermodynamic diagrams to understand the physics associated with the molecular-level self-assembly processes. Typical morphologies were observed, such as lamellar, spheroidal, cylindrical, gyroidal, and perforated lamellar, with the primary concentration region of the tethered particles being influenced heavily by particle size and tethering location, strength of the particle-segment energetic interactions, chain length, and copolymer radius of gyration. The effect of the simulation box size on the observed morphology and system thermodynamics was also investigated, indicating possible effects of confinement upon the system self-assembly processes.

  13. The effect of particle size on the morphology and thermodynamics of diblock copolymer/tethered-particle membranes.

    PubMed

    Zhang, Bo; Edwards, Brian J

    2015-06-07

    A combination of self-consistent field theory and density functional theory was used to examine the effect of particle size on the stable, 3-dimensional equilibrium morphologies formed by diblock copolymers with a tethered nanoparticle attached either between the two blocks or at the end of one of the blocks. Particle size was varied between one and four tenths of the radius of gyration of the diblock polymer chain for neutral particles as well as those either favoring or disfavoring segments of the copolymer blocks. Phase diagrams were constructed and analyzed in terms of thermodynamic diagrams to understand the physics associated with the molecular-level self-assembly processes. Typical morphologies were observed, such as lamellar, spheroidal, cylindrical, gyroidal, and perforated lamellar, with the primary concentration region of the tethered particles being influenced heavily by particle size and tethering location, strength of the particle-segment energetic interactions, chain length, and copolymer radius of gyration. The effect of the simulation box size on the observed morphology and system thermodynamics was also investigated, indicating possible effects of confinement upon the system self-assembly processes.

  14. Debendox revisited.

    PubMed

    Elbourne, D; Mutch, L; Dauncey, M; Campbell, H; Samphier, M

    1985-08-01

    Two further studies re-examine the findings by Golding et al. (1983) in Oxford that mothers of children born with oral clefts had been more frequently prescribed Debendox (Bendectin) than had the mothers of matched controls. In Cardiff, 86 283 total births between 1965 and 1979 included 139 infants with oral clefts. Detailed information was obtained about 93 of these infants and matched controls. The relative risk of the birth of an infant with an oral cleft to women prescribed Debendox within 69 days of the first day of their last menstrual period was 0.64 (95% confidence limits 0.12-3.34). No increased effect was found amongst women who smoked. In Aberdeen, 17 640 livebirths between 1976 and 1979 included 31 children with oral clefts. Compared with the non-exposed group the risk of a birth of an infant with an oral cleft to a woman prescribed Debendox in early pregnancy was 0.37 (95% confidence limits 0.09-1.47). These results do not confirm the previous findings in Oxford of a possible association between exposure to Debendox in early pregnancy and the occurrence of oral clefts in the child.

  15. Contextual learning and context effects during infancy: 30 years of controversial research revisited.

    PubMed

    Revillo, D A; Cotella, E; Paglini, M G; Arias, C

    2015-09-01

    Over the last 30years a considerable number of reports have explored learning about context during infancy in both humans and rats. This research was stimulated by two different theoretical frameworks. The first, known as the neuromaturational model, postulates that learning and behavior are context-independent during early ontogeny, a hypothesis based on the idea that contextual learning is dependent on the hippocampal function, and that this brain structure does not reach full maturity until late in infancy. The second theoretical framework views infants not as immature organisms, but rather as perfectly matured ones, given that their behavioral and cognitive capacities allow them to adapt appropriately to the demands of their specific environment in accordance with their maturational level. This model predicts significant ontogenetic variations in learning and memory due to developmental differences in what is perceived and attended to during learning episodes, which can result in ontogenetic differences in contextual learning depending on the specific demands of the task. The present manuscript reviews those studies that have examined potential developmental differences in contextual learning and context effects in rats. The reviewed results show that, during infancy, context can exert a similar influence over learning and memory as that described for the adult rat. Moreover, in some cases, contextual learning and context effects were greater in infants than in adults. In contrast, under other experimental conditions, no evidence of contextual learning or context effects was observed. We analyzed the procedural factors of these studies with the aim of detecting those that favor or impede contextual learning during infancy, and we discussed whether existing empirical evidence supports the claim that the functionality of the hippocampus is a limiting factor for this type of learning during infancy. Finally, conclusions from human research into contextual learning

  16. Strain engineering for mechanical properties in graphene nanoribbons revisited: The warping edge effect

    NASA Astrophysics Data System (ADS)

    Jiang, Jin-Wu

    2016-06-01

    We investigate the strain engineering and the edge effect for mechanical properties in graphene nanoribbons. The free edges of the graphene nanoribbons are warped due to compressive edge stresses. There is a structural transformation for the free edges from the three-dimensional warping configuration to the two-dimensional planar structure at the critical strain ɛc = 0.7%, at which the applied mechanical stress is equal to the intrinsic compressive edge stress. This structural transformation leads to step-like changes in several mechanical properties studied in the present work, including the Young's modulus, the Poisson's ratio, the quality factor of nanomechanical resonators, and the phonon edge mode.

  17. The effect of HMOs on fee-for-service health care expenditures: evidence from Medicare revisited.

    PubMed

    Batata, Amber

    2004-09-01

    This paper implements a new method for calculating the extent of selection in the aged Medicare HMO market. Selection is measured as the difference in average costs between new Medicare HMO enrollees and Medicare fee-for-service stayers with data from 1990 to 1994. Results suggest Medicare HMO enrollees were 1030 US dollars cheaper in their first year of enrollment. The effect is found entirely in Part A (hospital) expenditures, confirming selection is based on inpatient rather than outpatient or preventive care. These results are consistent with previous work.

  18. Dynamic causal modelling revisited.

    PubMed

    Friston, K J; Preller, Katrin H; Mathys, Chris; Cagnan, Hayriye; Heinzle, Jakob; Razi, Adeel; Zeidman, Peter

    2017-02-17

    This paper revisits the dynamic causal modelling of fMRI timeseries by replacing the usual (Taylor) approximation to neuronal dynamics with a neural mass model of the canonical microcircuit. This provides a generative or dynamic causal model of laminar specific responses that can generate haemodynamic and electrophysiological measurements. In principle, this allows the fusion of haemodynamic and (event related or induced) electrophysiological responses. Furthermore, it enables Bayesian model comparison of competing hypotheses about physiologically plausible synaptic effects; for example, does attentional modulation act on superficial or deep pyramidal cells - or both? In this technical note, we describe the resulting dynamic causal model and provide an illustrative application to the attention to visual motion dataset used in previous papers. Our focus here is on how to answer long-standing questions in fMRI; for example, do haemodynamic responses reflect extrinsic (afferent) input from distant cortical regions, or do they reflect intrinsic (recurrent) neuronal activity? To what extent do inhibitory interneurons contribute to neurovascular coupling? What is the relationship between haemodynamic responses and the frequency of induced neuronal activity? This paper does not pretend to answer these questions; rather it shows how they can be addressed using neural mass models of fMRI timeseries.

  19. Predator interference effects on biological control: The "paradox" of the generalist predator revisited

    NASA Astrophysics Data System (ADS)

    Parshad, Rana D.; Bhowmick, Suman; Quansah, Emmanuel; Basheer, Aladeen; Upadhyay, Ranjit Kumar

    2016-10-01

    An interesting conundrum in biological control questions the efficiency of generalist predators as biological control agents. Theory suggests, generalist predators are poor agents for biological control, primarily due to mutual interference. However field evidence shows they are actually quite effective in regulating pest densities. In this work we provide a plausible answer to this paradox. We analyze a three species model, where a generalist top predator is introduced into an ecosystem as a biological control, to check the population of a middle predator, that in turn is depredating on a prey species. We show that the inclusion of predator interference alone, can cause the solution of the top predator equation to blow-up in finite time, while there is global existence in the no interference case. This result shows that interference could actually cause a population explosion of the top predator, enabling it to control the target species, thus corroborating recent field evidence. Our results might also partially explain the population explosion of certain species, introduced originally for biological control purposes, such as the cane toad (Bufo marinus) in Australia, which now functions as a generalist top predator. We also show both Turing instability and spatio-temporal chaos in the model. Lastly we investigate time delay effects.

  20. Revisiting the controversial role of salsolinol in the neurobiological effects of ethanol: old and new vistas.

    PubMed

    Hipólito, Lucía; Sánchez-Catalán, María José; Martí-Prats, Lucía; Granero, Luis; Polache, Ana

    2012-01-01

    The possible involvement of salsolinol (Sal), an endogenous condensation product of ACD (the first metabolite of ethanol) and dopamine, in the neurochemical basis underlying ethanol action has been repeatedly suggested although it has not been unequivocally established, still being a controversial matter of debate. The main goal of this review is to evaluate the presumed contribution of Sal to ethanol effects summarizing the reported data since the discovery in the 1970s of Sal formation in vitro during ethanol metabolism until the more recent studies characterizing its behavioral and neurochemical effects. Towards this end, we first analyze the production and detection of Sal, in different brain areas, in basal conditions and after alcohol consumption, highlighting its presence in regions especially relevant in regulating ethanol-drinking behaviour and the importance of the newly developed methods to differentiate both enantiomers of Sal which could help to explain some previous negative findings. Afterwards, we review the behavioral and neurochemical studies. Finally, we present and discuss the previous and current enunciated mechanisms of action of Sal in the CNS.

  1. Obesity by choice revisited: effects of food availability, flavor variety and nutrient composition on energy intake.

    PubMed

    Ackroff, Karen; Bonacchi, Kristine; Magee, Michael; Yiin, Yeh-Min; Graves, Jonathan V; Sclafani, Anthony

    2007-10-22

    Recent work suggested that the energy intake and weight gain of rats maintained on chow and 32% sucrose solution could be increased by simply offering more sources of sucrose [Tordoff M.G. Obesity by choice: the powerful influence of nutrient availability on nutrient intake. Am J Physiol 2002;282:R1536-R1539.]. In Experiment 1 this procedure was replicated but the effect was not: rats given one bottle of sucrose and five bottles of water consumed as much sucrose as those given five bottles of sucrose and one of water. Adding different flavors to the sucrose did not increase intakes further in Experiment 2. The relative potency of sucrose and other optional foods was studied in Experiment 3. Sucrose solution stimulated more overeating and weight gain than fat (vegetable shortening), and offering both sucrose and shortening did not generate further increases in energy intake. Finally, foods commonly used to produce overeating and weight gain were compared. Sucrose was less effective than a high-fat milk diet, and offering cookies in addition to the milk did not increase energy intake further. The nature of optional foods (nutrient composition and physical form) was markedly more important than the number of food sources available to the animals, and is a better contender as the reason for "obesity by choice".

  2. Depth effect on lightness revisited: The role of articulation, proximity and fields of illumination

    PubMed Central

    Radonjić, Ana; Gilchrist, Alan L.

    2013-01-01

    The coplanar ratio principle proposes that when the luminance range in an image is larger than the canonical reflectance range of 30:1, the lightness of a target surface depends on the luminance ratio between that target and its adjacent coplanar neighbor (Gilchrist, 1980). This conclusion is based on experiments in which changes in the perceived target depth produced large changes in its perceived lightness without significantly altering the observers' retinal image. Using the same paradigm, we explored how this depth effect on lightness depends on display complexity (articulation), proximity of the target to its highest coplanar luminance and spatial distribution of fields of illumination. Importantly, our experiments allowed us to test differing predictions made by the anchoring theory (Gilchrist et al., 1999), the coplanar ratio principle, as well as other models. We report three main findings, generally consistent with anchoring theory predictions: (1) Articulation can substantially increase the depth effect. (2) Target lightness depends not on the adjacent luminance but on the highest coplanar luminance, irrespective of its position relative to the target. (3) When a plane contains multiple fields of illumination, target lightness depends on the highest luminance in its field of illumination, not on the highest coplanar luminance. PMID:24349701

  3. The Community College Effect Revisited: The Importance of Attending to Heterogeneity and Complex Counterfactuals*

    PubMed Central

    Brand, Jennie E.; Pfeffer, Fabian T.; Goldrick-Rab, Sara

    2015-01-01

    Community colleges are controversial educational institutions, often said to simultaneously expand college opportunities and diminish baccalaureate attainment. We assess the seemingly contradictory functions of community colleges by attending to effect heterogeneity and to alternative counterfactual conditions. Using data on postsecondary outcomes of high school graduates of Chicago Public Schools, we find that enrolling at a community college penalizes more advantaged students who otherwise would have attended four-year colleges, particularly highly selective schools; however, these students represent a relatively small portion of the community college population, and these estimates are almost certainly biased. On the other hand, enrolling at a community college has a modest positive effect on bachelor's degree completion for disadvantaged students who otherwise would not have attended college; these students represent the majority of community college goers. We conclude that discussions among scholars, policymakers, and practitioners should move beyond considering the pros and cons of community college attendance for students in general to attending to the implications of community college attendance for targeted groups of students. PMID:25825705

  4. Thermodynamic analysis of effects of contact angle on interfacial interactions and its implications for membrane fouling control.

    PubMed

    Chen, Jianrong; Shen, Liguo; Zhang, Meijia; Hong, Huachang; He, Yiming; Liao, Bao-Qiang; Lin, Hongjun

    2016-02-01

    Concept of hydrophobicity always fails to accurately assess the interfacial interaction and membrane fouling, which calls for reliable parameters for this purpose. In this study, effects of contact angle on interfacial interactions related to membrane fouling were investigated based on thermodynamic analysis. It was found that, total interaction energy between sludge foulants and membrane monotonically decreases and increases with water and glycerol contact angle, respectively, indicating that these two parameters can be reliable indicators predicting total interaction energy and membrane fouling. Membrane roughness decreases interaction strength for over 20 times, and effects of membrane roughness on membrane fouling should consider water and glycerol contact angle on membrane. It was revealed existence of a critical water and glycerol contact angle for a given membrane bioreactor. Meanwhile, diiodomethane contact angle has minor effect on the total interaction, and cannot be regarded as an effective indicator assessing interfacial interactions and membrane fouling.

  5. Revisit of basal effective friction and pore pressure for Japan trench from topographic point of view

    NASA Astrophysics Data System (ADS)

    Koge, H.; Fujiwara, T.; Kodaira, S.; Sasaki, T.; Kameda, J.; Hamahashi, M.; Hamada, Y.; Kimura, G.

    2013-12-01

    2011 Tohoku-oki earthquake (Mw9.0) produced a fault rupture, extending to the shallow part of the Japan Trench. Based on the bathymetry difference before and after the earthquake, it is demonstrated that the seafloor on outermost landward slope moved ~50 m east-southeastward towards the trench and uplifted ~7 to 10 m. Although the mechanism of the fault rupture is not clear, deformation and frictional properties beneath the forearc are the key to elucidate this important issue. Kimura et al (2012) focused on seismic reflection data along one seismic transect at the Japan Trench (name the transect), and calculated the basal effective friction of the plate boundary by using the critical taper theory. Limited profiles from narrow area, however, never represent general friction property of the plate boundary in the Japan trench. Therefore, several profiles are examined to investigate for the better understanding along-trench variation of the basal frictional properties. Bathymetric and seismic reflection data were taken before and after the Tohoku-oki earthquake to obtain the following angles; slope angle of upper surface, basal dip of the outer wedge. Acuired angles are limited to only the lowest trench slope of the Japan Trench. The limitation enables us to treat the wedge as a more uniform body than would have been achieved with the whole range of seismic cross sections. Applying the critical taper theory to the individual seismic cross sections, force balance among the interior and base of the wedge, fluid pressure ratio, and the basal effective friction of the plate boundary are calculated. Additionally, by using "earth pressure theory", we estimated basal effective friction of ~0.15 under the assumption that branching faults act as back-stops in lower slope areas. References Cubas et al., Geophysical Research Letters: DOI:10.1002/grl.50682 Fujiwara et al., Science 2 December 2011: Vol. 334 no. 6060 p. 1240 Wang and Hu, Journal of Geophysical Research, v.111, p1

  6. Effects of confinement between attractive and repulsive walls on the thermodynamics of an anomalous fluid.

    PubMed

    Leoni, Fabio; Franzese, Giancarlo

    2016-12-01

    We study via molecular-dynamics simulations the thermodynamics of an anomalous fluid confined in a slit pore with one wall structured and attractive and another unstructured and repulsive. We find that the phase diagram of the homogeneous part of the confined fluid is shifted to higher temperatures, densities, and pressures with respect to the bulk, but it can be rescaled on the bulk case. We calculate a moderate increase of mobility of the homogeneous confined fluid that we interpret as a consequence of the layering due to confinement and the collective modes due to long-range correlations. We show that, as in bulk, the confined fluid has structural, diffusion, and density anomalies that order in the waterlike hierarchy, and a liquid-liquid critical point (LLCP). The overall anomalous region moves to higher temperatures, densities, and pressure, and the LLCP displaces to higher temperature compared to bulk. Motivated by experiments, we calculate also the phase diagram not just for the homogeneous part of the confined fluid but for the entire fluid in the pore, and we show that it is shifted toward higher pressures but preserves the thermodynamics, including the LLCP. Because our model has waterlike properties, we argue that in experiments with supercooled water confined in slit pores with a width of >3 nm if hydrophilic and of >1.5 nm if hydrophobic, the existence of the LLCP could be easier to test than in bulk, where it is not directly accessible.

  7. Inviscid spatial stability of a compressible mixing layer. Part 3: Effect of thermodynamics

    NASA Technical Reports Server (NTRS)

    Jackson, T. L.; Grosch, C. E.

    1989-01-01

    The results of a comprehensive comparative study of the inviscid spatial stability of a parallel compressible mixing layer using various models for the mean flow are reported. The models are: (1) the hyperbolic tangent profile for the mean speed and the Crocco relation for the mean temperature, with the Chapman viscosity-temperature relation and a Prandtl number of one; (2) the Lock profile for the mean speed and the Crocco relation for the mean temperature, with the Chapman viscosity-temperature relation and a Prandtl number of one; and (3) the similarity solution for the coupled velocity and temperature equations using the Sutherland viscosity temperature relation and arbitrary but constant Prandtl number. The purpose was to determine the sensitivity of the stability characteristics of the compressible mixing layer to the assumed thermodynamic properties of the fluid. It is shown that the quantative features of the stability characteristics are quite similiar for all models but that there are quantitative differences resulting from the difference in the thermodynamic models. In particular, it is shown that the stability characteristics are sensitive to the value of the Prandtl number.

  8. Effects of confinement between attractive and repulsive walls on the thermodynamics of an anomalous fluid

    NASA Astrophysics Data System (ADS)

    Leoni, Fabio; Franzese, Giancarlo

    2016-12-01

    We study via molecular-dynamics simulations the thermodynamics of an anomalous fluid confined in a slit pore with one wall structured and attractive and another unstructured and repulsive. We find that the phase diagram of the homogeneous part of the confined fluid is shifted to higher temperatures, densities, and pressures with respect to the bulk, but it can be rescaled on the bulk case. We calculate a moderate increase of mobility of the homogeneous confined fluid that we interpret as a consequence of the layering due to confinement and the collective modes due to long-range correlations. We show that, as in bulk, the confined fluid has structural, diffusion, and density anomalies that order in the waterlike hierarchy, and a liquid-liquid critical point (LLCP). The overall anomalous region moves to higher temperatures, densities, and pressure, and the LLCP displaces to higher temperature compared to bulk. Motivated by experiments, we calculate also the phase diagram not just for the homogeneous part of the confined fluid but for the entire fluid in the pore, and we show that it is shifted toward higher pressures but preserves the thermodynamics, including the LLCP. Because our model has waterlike properties, we argue that in experiments with supercooled water confined in slit pores with a width of >3 nm if hydrophilic and of >1.5 nm if hydrophobic, the existence of the LLCP could be easier to test than in bulk, where it is not directly accessible.

  9. Protein–Ligand Interactions: Thermodynamic Effects Associated with Increasing the Length of an Alkyl Chain

    PubMed Central

    2013-01-01

    Thermodynamic parameters were determined for complex formation between the Grb2 SH2 domain and tripeptides of the general form Ac-pTyr-Xaa-Asn in which the Xaa residue bears a linear alkyl chain varying in length from 1–5 carbon atoms. Binding affinity increases upon adding a methylene group to the Ala derivative, but further chain extension gives no extra enhancement in potency. The thermodynamic signatures of the ethyl and n-propyl derivatives are virtually identical as are those for the n-butyl and n-pentyl analogues. Crystallographic analysis of the complexes reveals a high degree of similarity in the structure of the domain and the bound ligands with the notable exception that there is a gauche interaction in the side chains in the bound conformations of ligands having n-propyl, n-butyl, and n-pentyl groups. However, eliminating this unfavorable interaction by introducing a Z-double bond into the side chain of the n-propyl analogue does not result in an increase in affinity. Increases in the amount of nonpolar surface that is buried upon ligand binding correlate with favorable changes in ΔH°, but these are usually offset by corresponding unfavorable changes in −TΔS°; there is little correlation of ΔCp with changes in the amount of buried nonpolar surface. PMID:24349642

  10. Effect of long- and short-range interactions on the thermodynamics of dipolar spin ice

    NASA Astrophysics Data System (ADS)

    Shevchenko, Yuriy; Makarov, Aleksandr; Nefedev, Konstantin

    2017-02-01

    The thermodynamic properties of dipolar spin ice on square, honeycomb and shakti lattices in the long-range and short-range dipole interaction models are studied. Exact solutions for the density of states, temperature dependencies of heat capacity, and entropy are obtained for these lattices with a finite number of point dipoles by means of complete enumeration. The magnetic susceptibility and average size of the largest low-energy cluster are calculated for square spin ice by means of Wang-Landau and Metropolis methods. We show that the long-range interaction leads to a blurring of the energy spectrum for all considered lattices. The inclusion of the long-range interaction leads to a significant change in the thermodynamic behaviour. An additional peak of heat capacity appears in the case of the honeycomb lattice. The critical temperature shifts in the direction of low or high temperatures; the direction depends on the lattice geometry. The critical temperature of the phase transition of square spin ice in the long-range model with frustrated ground states is obtained with the Wang-Landau and Metropolis methods independently.

  11. Effects of Calcium Ions on Thermodynamic Properties of Mixed Bilirubin/Cholesterol Monolayers

    NASA Astrophysics Data System (ADS)

    Wu, Qiong; Tang, Yu-feng; Li, Ye-min; Xie, An-jian; Shen, Yu-hua; Zhu, Jin-miao; Li, Chuan-hao

    2008-04-01

    The mixed monolayer behavior of bilirubin/cholesterol was studied through surface pressure-area (π-A) isotherms on aqueous solutions containing various concentrations of calcium ions. Based on the data of π-A isotherms, the mean area per molecule, collapse pressure, surface compressibility modulus, excess molecular areas, free energy of mixing, and excess free energy of mixing of the monolayers on different subphases were calculated. The results show an expansion in the structure of the mixed monolayer with Ca2+ in subphase, and non-ideal mixing of the components at the air/water interface is observed with positive deviation from the additivity rule in the excess molecular areas. The miscibility between the components is weakened with the increase of concentration of Ca2+ in subphase. The facts indicate the presence of coordination between Ca2+ and the two components. The mixed monolayer, in which the molar ratio of bilirubin to cholesterol is 3:2, is more stable from a thermodynamic point of view on pure water. But the stable 3:2 stoichiometry complex is destroyed with the increase of the concentration of Ca2+ in subphase. Otherwise, the mixed monolayers have more thermodynamic stability at lower surface pressure on Ca2+ subphase.

  12. Radiation effects on the MHD flow near the stagnation point of a stretching sheet: revisited

    NASA Astrophysics Data System (ADS)

    Pop, Ioan; Ishak, Anuar; Aman, Fazlina

    2011-10-01

    This paper considers the effects of radiation on the flow near the two-dimensional stagnation point of a stretching sheet immersed in a viscous and incompressible electrically conducting fluid in the presence of an applied constant magnetic field. The external velocity and the stretching velocity of the sheet are assumed to vary linearly with the distance from the stagnation point. The governing partial differential equations are transformed into a system of ordinary differential equations using a similarity transformation, before being solved numerically by the Keller-box method. The features of the heat transfer characteristics for different values of the governing parameters are analyzed and discussed. The results indicate that the heat transfer rate at the surface decreases in the presence of radiation.

  13. The Reverse-Caricature Effect Revisited: Familiarization With Frontal Facial Caricatures Improves Veridical Face Recognition

    PubMed Central

    RODRÍGUEZ, JOBANY; BORTFELD, HEATHER; RUDOMÍN, ISAAC; HERNÁNDEZ, BENJAMÍN; GUTIÉRREZ-OSUNA, RICARDO

    2010-01-01

    SUMMARY Prior research suggests that recognition of a person's face can be facilitated by exaggerating the distinctive features of the face during training. We tested if this ‘reverse-caricature effect’ would be robust to procedural variations that created more difficult learning environments. Specifically, we examined whether the effect would emerge with frontal rather than three-quarter views, after very brief exposure to caricatures during the learning phase and after modest rotations of faces during the recognition phase. Results indicate that, even under these difficult training conditions, people are more accurate at recognizing unaltered faces if they are first familiarized with caricatures of the faces, rather than with the unaltered faces. These findings support the development of new training methods to improve face recognition. PMID:21132058

  14. Position-effect variegation revisited: HUSHing up heterochromatin in human cells.

    PubMed

    Timms, Richard T; Tchasovnikarova, Iva A; Lehner, Paul J

    2016-04-01

    Much of what we understand about heterochromatin formation in mammals has been extrapolated from forward genetic screens for modifiers of position-effect variegation (PEV) in the fruit fly Drosophila melanogaster. The recent identification of the HUSH (Human Silencing Hub) complex suggests that more recent evolutionary developments contribute to the mechanisms underlying PEV in human cells. Although HUSH-mediated repression also involves heterochromatin spreading through the reading and writing of the repressive H3K9me3 histone modification, clear orthologues of HUSH subunits are not found in Drosophila but are conserved in vertebrates. Here we compare the insights into the mechanisms of PEV derived from genetic screens in the fly, the mouse and in human cells, review what is currently known about the HUSH complex and discuss the implications of HUSH-mediated silencing for viral latency. Future studies will provide mechanistic insight into HUSH complex function and reveal the relationship between HUSH and other epigenetic silencing complexes.

  15. Freezing tolerance revisited-effects of variable temperatures on gene regulation in temperate grasses and legumes.

    PubMed

    Kovi, Mallikarjuna Rao; Ergon, Åshild; Rognli, Odd Arne

    2016-10-01

    Climate change creates new patterns of seasonal climate variation with higher temperatures, longer growth seasons and more variable winter climates. This is challenging the winter survival of perennial herbaceous plants. In this review, we focus on the effects of variable temperatures during autumn/winter/spring, and its interactions with light, on the development and maintenance of freezing tolerance. Cold temperatures induce changes at several organizational levels in the plant (cold acclimation), leading to the development of freezing tolerance, which can be reduced/lost during warm spells (deacclimation) in winters, and attained again during cold spells (reacclimation). We summarize how temperature interacts with components of the light regime (photoperiod, PSII excitation pressure, irradiance, and light quality) in determining changes in the transcriptome, proteome and metabolome.

  16. Cadmium chloride toxicity revisited: effect on certain andrological, endocrinological and biochemical parameters of adult male rabbits.

    PubMed

    Sajjad, S; Malik, H; Farooq, U; Rashid, F; Nasim, H; Tariq, S; Rehman, S

    2014-01-01

    The present study was devised to assess the effects of cadmium chloride (CdCl(2)) administration on certain andrological, endocrinological and biochemical alterations in adult male rabbits (n=24). The animals were assigned to control (n=8) and experimental (n=16) group. Experimental group was orally administered with 1.5 mg/kg body weight of CdCl(2). The trials were carried out for a total of 5 weeks and blood sampling was carried out on weekly basis. A gradual decrease was noticed for body weight in the experimental group from week 1 to 5, being significantly lower in week 4 and 5 (P<0.05). A similar decremented trend was noticed for serum testosterone level being significantly lower in experimental group in week 4 and 5 (P<0.001). Significantly lower values were noticed for prolactin in experimental group in week 4 and 5 (P<0.05), than in the control. On the contrary, serum cortisol level showed a gradual increase in experimental group, from week 1 to 5, being significantly higher in week 4 and 5 (P<0.05). Regarding the biochemical attributes, all the parameters under study revealed a gradually ascending trend. Statistical significance was, however, achieved in varying weeks and at varying levels. The total protein and albumin were significantly higher in week 4 and 5 (P<0.01); alanine aminotransferase in week 2 (P<0.01), 3 (P<0.001), 4 (P<0.01) and 5 (P<0.001); aspartate aminotransferase in week 1, 2, 3, 4 and 5 (P<0.01); and alkaline phosphatase in week 1, 2 (P<0.01), 3, 4 and 5 (P<0.0001), respectively. Overall mortality rate in experimental group was 68.75 (11/16). In a nutshell, Cd exposure results in adverse effects on all physiological parameters of body and may lead to lethal consequences.

  17. Panspermia revisited

    NASA Astrophysics Data System (ADS)

    Horneck, Gerda

    "Panspermia", coined by S. Arrhenius in 1903, suggests that microscopic forms of life, e.g., bacterial spores, can be dispersed in space by the radiation pressure from the Sun thereby seeding life from one planet to another or even beyond our Solar System. Being ignored for almost the rest of the century, the scenario of interplanetary transfer of life has received increased support from recent discoveries, such as the detection of Martian meteorites and the high resistance of microorganisms to outer space conditions. With the aid of space technology and adequate laboratory devices the following decisive step required for viable transfer from one planet to another have been tested: (i) the escape process, i.e. impact ejection into space; (ii) the journey through space over extended periods of time; and (iii) the landing process, i.e. non-destructive deposition of the biological material on another planet. In systematic shock recovery experiments within a pressure range observed in Martian meteorites (5-50 GPa) a vital launch window of 5-40 GPa has been determined for spores of Bacillus subtilis and the lichen Xanthoria elegans, whereas this window was restricted to 5-10 GPa for the endolithic cyanobaterium Chroococcidiopsis. Traveling through space implies exposure to high vacuum, an intense radiation regime of cosmic and solar origin and high temperature fluctuations. In several space experiments the biological efficiency of these different space parameters has been tested: extraterrestrial solar UV radiation has exerted the most deleterious effects to viruses, as well as to bacterial and fungal spores; however shielding against this intense insolation resulted in 70 % survival of B. subtilis spores after spending 6 years in outer space. Lichens survived 2 weeks in space, even without any shielding. The entry process of microorganisms has been recently tested in the STONE facility attached to the heat shield of a reentry capsule. The data support the scenario of

  18. The jamming transition in high dimension: an analytical study of the TAP equations and the effective thermodynamic potential

    NASA Astrophysics Data System (ADS)

    Altieri, Ada; Franz, Silvio; Parisi, Giorgio

    2016-09-01

    We present a parallel derivation of the Thouless-Anderson-Palmer (TAP) equations and of an effective thermodynamic potential for the negative perceptron and soft sphere models in high dimension. Both models are continuous constrained satisfaction problems with a critical jamming transition characterized by the same exponents. Our analysis reveals that a power expansion of the potential up to the second order constitutes a successful framework to approach the jamming points from the SAT phase (the region of the phase diagram where at least one configuration verifies all the constraints), where the ground-state energy is zero. An interesting outcome is that approaching the jamming line the effective thermodynamic potential has a logarithmic contribution, which turns out to be dominant in a proper scaling regime. Our approach is quite general and can be directly applied to other interesting models. Finally we study the spectrum of small harmonic fluctuations in the SAT phase recovering the typical scaling D(ω )˜ {ω2} below the cutoff frequency but a different behavior characterized by a non-trivial exponent above it.

  19. Study of wetting on chemically soften interfaces by using combined solution thermodynamics and DFT calculations: forecasting effective softening elements.

    PubMed

    Shu, Guo Gang; Xu, Qiang; Wu, Ping

    2015-04-15

    Despite recent progress in understanding the wetting principles on soft solids, the roles of chemical bonding in the formation of interfaces have been largely ignored, because most of these studies are conducted at room temperatures. Here we propose a universal wetting principle from solution thermodynamics to account for the softening of both the solid and liquid surfaces (stable or metastable). Density functional theory (DFT) calculations are applied to evaluate the stability and electron transportation across the interfaces. We find that wetting is dominated by the system entropy changes involving not only the stable liquid alloy phase but also the metastable liquid oxide phases. The state-of-art multicomponent solution thermodynamic models and databases are applied to describe the entropy changes and predict the wetting behaviors. Our results show that by chemically softening either the liquid or the solid phase, the wetting angle reduces. And an effective soften agent/additive (either in the form of chemical elements or molecules) will weaken the bonds within the liquid (or solid) phase and promote new bonds at the interfaces, thus increasing the interface entropy. Subsequently, as an example, Ti and Zr are proposed as effective softening elements to improve the wetting of aluminum liquid on B6Si(s). This approach provides a concept and tool to advance research in catalytic chemistry, nucleation (growth), elastowetting, and cell-substrate interactions.

  20. The Influence of the Effect of Solute on the Thermodynamic Driving Force on Grain Refinement of Al Alloys

    NASA Astrophysics Data System (ADS)

    Wang, Feng; Liu, Zhi-Lin; Qiu, Dong; Taylor, John A.; Easton, Mark A.; Zhang, Ming-Xing

    2015-01-01

    Grain refinement is known to be strongly affected by the solute in cast alloys. Addition of some solute can reduce grain size considerably while others have a limited effect. This is usually attributed to the constitutional supercooling which is quantified by the growth restriction factor, Q. However, one factor that has not been considered is whether different solutes have differing effects on the thermodynamic driving force for solidification. This paper reveals that addition of solute reduces the driving force for solidification for a given undercooling, and that for a particular Q value, it is reduced more substantially when adding eutectic-forming solutes than peritectic-forming elements. Therefore, compared with the eutectic-forming solutes, addition of peritectic-forming solutes into Al alloys not only possesses a higher initial nucleation rate resulted from the larger thermodynamic driving force for solidification, but also promotes nucleation within the constitutionally supercooled zone during growth. As subsequent nucleation can occur at smaller constitutional supercoolings for peritectic-forming elements, a smaller grain size is thus produced. The very small constitutional supercooling required to trigger subsequent nucleation in alloys containing Ti is considered as a major contributor to its extraordinary grain refining efficiency in cast Al alloys even without the deliberate addition of inoculants.

  1. Revisiting the effectiveness of methadone treatment on crime reductions in the 1990s.

    PubMed

    Rothbard, A; Alterman, A; Rutherford, M; Liu, F; Zelinski, S; McKay, J

    1999-06-01

    This study examines the relationship between methadone treatment and the criminal activity of 126 individuals participating in treatment during the early 1990s. The primary question addressed is to what extent is methadone maintenance treatment associated with reductions in crime? Although prior studies in the 1970s and early 1980s showed significant decreases in crime for individuals in treatment programs, criteria for remaining in this treatment modality have changed in recent years, particularly with the advent of acquired immune deficiency syndrome and the need to reduce intravenous drug use. A pre-post study design is employed spanning a 6-year time period of subject recruitment and follow-up (1987-1993). Uniform administrative records on arrests are used for the analyses. A multiple regression model is employed to explain the variance in the number of arrests 2 years following program admission, with prior criminal history, prior and current drug treatment, and current cocaine use employed as explanatory variables. Results indicate that treatment retention has only a slight, though significant, effect on reducing criminal activity during treatment. Two other factors that appear to increase arrest activity are the use of cocaine and prior criminal history. The fact that arrests did not decrease during a treatment period of 18 months on average requires more investigation in light of the increase in cocaine use in this population.

  2. Between-person effects on attention and action: Joe and Fred revisited.

    PubMed

    Hayes, Spencer J; Hansen, Steve; Elliott, Digby

    2010-05-01

    Previous study indicates that target-target inhibition of return (IOR) is not restricted to a single nervous system. Specifically, watching another person perform a goal-directed aiming movement engages similar inhibitory processes on a subsequent aiming attempt as if having performed the preceding movement oneself. This between-person effect has been attributed to the mirror neuron system. In the study reported here, we replicated this finding and examined the relative importance of automatic stimulus alerting events and action-observation by dissociating these two influences. This was done by having two people alternately perform sets of two aiming trials to the same equally probable targets. Under some experimental conditions, one or both of the performers moved to a non-illuminated target. In this way, we dissociated the stimulus and observed event under some between-person conditions. Although IOR was greatest when the stimulus and observed events were compatible, both contributed to the between-person inhibitory processes slowing the responses (Experiment 1). The impact of observing another person perform an aiming movement appears to have more to do with realizing a particular spatial goal than seeing the biological motion associated with achieving that goal (Experiment 2). Findings that both the illumination of a visual target signal and the observation of another person's action engage similar attention-action processes are consistent with action-based accounts of visual selective attention.

  3. Revisiting Aerosol Effects in Global Climate Models Using an Aerosol Lidar Simulator

    NASA Astrophysics Data System (ADS)

    Ma, P. L.; Chepfer, H.; Winker, D. M.; Ghan, S.; Rasch, P. J.

    2015-12-01

    Aerosol effects are considered a major source of uncertainty in global climate models and the direct and indirect radiative forcings have strong model dependency. These forcings are routinely evaluated (and calibrated) against observations, among them satellite retrievals are greatly used for their near-global coverage. However, the forcings calculated from model output are not directly comparable with those computed from satellite retrievals since sampling and algorithmic differences (such as cloud screening, noise reduction, and retrieval) between models and observations are not accounted for. It is our hypothesis that the conventional model validation procedures for comparing satellite observations and model simulations can mislead model development and introduce biases. Hence, we have developed an aerosol lidar simulator for global climate models that simulates the CALIOP lidar signal at 532nm. The simulator uses the same algorithms as those used to produce the "GCM-oriented CALIPSO Aerosol Product" to (1) objectively sample lidar signal profiles; and (2) derive aerosol fields (e.g., extinction profile, aerosol type, etc) from lidar signals. This allows us to sample and derive aerosol fields in the model and real atmosphere in identical ways. Using the Department of Energy's ACME model simulations, we found that the simulator-retrieved aerosol distribution and aerosol-cloud interactions are significantly different from those computed from conventional approaches, and that the model is much closer to satellite estimates than previously believed.

  4. Moose body mass variation revisited: disentangling effects of environmental conditions and genetics.

    PubMed

    Herfindal, Ivar; Haanes, Hallvard; Solberg, Erling J; Røed, Knut H; Høgda, Kjell Arild; Sæther, Bernt-Erik

    2014-02-01

    Large-scale geographical variation in phenotypic traits within species is often correlated to local environmental conditions and population density. Such phenotypic variation has recently been shown to also be influenced by genetic structuring of populations. In ungulates, large-scale geographical variation in phenotypic traits, such as body mass, has been related to environmental conditions and population density, but little is known about the genetic influences. Research on the genetic structure of moose suggests two distinct genetic lineages in Norway, structured along a north-south gradient. This corresponds with many environmental gradients, thus genetic structuring provides an additional factor affecting geographical phenotypic variation in Norwegian moose. We investigated if genetic structure explained geographical variation in body mass in Norwegian moose while accounting for environmental conditions, age and sex, and if it captured some of the variance in body mass that previously was attributed to environmental factors. Genetic structuring of moose was the most important variable in explaining the geographic variation in body mass within age and sex classes. Several environmental variables also had strong explanatory power, related to habitat diversity, environmental seasonality and winter harshness. The results suggest that environmental conditions, landscape characteristics, and genetic structure should be evaluated together when explaining large-scale patterns in phenotypic characters or life history traits. However, to better understand the role of genetic and environmental effects on phenotypic traits in moose, an extended individual-based study of variation in fitness-related characters is needed, preferably in an area of convergence between different genetic lineages.

  5. The Raspberry model for hydrodynamic interactions revisited. II. The effect of confinement

    NASA Astrophysics Data System (ADS)

    de Graaf, Joost; Peter, Toni; Fischer, Lukas P.; Holm, Christian

    2015-08-01

    The so-called "raspberry" model refers to the hybrid lattice-Boltzmann (LB) and Langevin molecular dynamics schemes for simulating the dynamics of suspensions of colloidal particles, originally developed by Lobaskin and Dünweg [New J. Phys. 6, 54 (2004)], wherein discrete surface points are used to achieve fluid-particle coupling. In this paper, we present a follow up to our study of the effectiveness of the raspberry model in reproducing hydrodynamic interactions in the Stokes regime for spheres arranged in a simple-cubic crystal [Fischer et al., J. Chem. Phys. 143, 084107 (2015)]. Here, we consider the accuracy with which the raspberry model is able to reproduce such interactions for particles confined between two parallel plates. To this end, we compare our LB simulation results to established theoretical expressions and finite-element calculations. We show that there is a discrepancy between the translational and rotational mobilities when only surface coupling points are used, as also found in Part I of our joint publication. We demonstrate that adding internal coupling points to the raspberry can be used to correct said discrepancy in confining geometries as well. Finally, we show that the raspberry model accurately reproduces hydrodynamic interactions between a spherical colloid and planar walls up to roughly one LB lattice spacing.

  6. Thermoset recycling via high-pressure high-temperature sintering: Revisiting the effect of interchange chemistry

    NASA Astrophysics Data System (ADS)

    Morin, Jeremy Edward

    In 1844 Charles Goodyear obtained U.S. Patent #3,633 for his "Gum Elastic Composition". In a published circular, which describes his patent for the sulfur vulcanization of gum elastic composition, he stated: "No degree of heat, without blaze, can melt it (rubber)... It resists the most powerful chemical reagents. Aquafortis (nitric acid), sulphuric acid, essential and common oils, turpentine and other solvents... ..." Goodyear's sulfur vulcanization of rubber fueled much of the industrial revolution and made transportation possible, as it exists today. In doing so, Goodyear created one of the most difficult materials to recycle. Rubber will not melt, dissolve, or lend itself to the usual methods of chemical decomposition. Ironically, Goodyear recognized this problem and in 1853 he patented the process of adding ground rubber to virgin material, now currently known as regrind blending. Today, scrap tires represent one of the most serious sources of pollution in the world. Studies estimate that there are roughly 2 billion scrap tires in U.S. landfills and more are being added at a rate of over 273 million tires per year. Current methods of recycling waste tires are crude, ineffective, and use rubber powder as a low cost filler instead of a new rubber. The groundwork for a very simple and effective method of producing high-quality rubber goods using 100% scrap rubber was discovered in 1944 by A. V. Tobolsky et al. This application, however, was not recognized until recently in our laboratory. The process as studied to date represents a method of creating quality, high-value added rubber goods with nothing other than heat and pressure. High pressure is required to obtain a void-free compaction of the rubber particles by forcing all of the free surfaces into intimate contact. High temperature then activates the chemical rearrangement, scission, and reformation of the chemical bonds thus providing new bridges between the once fractured interfaces. This occurs both within

  7. Thermodynamics and dynamics of phosphatidylcholine-cholesterol mixed model membranes in the liquid crystalline state: effects of water.

    PubMed Central

    Shin, Y K; Budil, D E; Freed, J H

    1993-01-01

    A method for obtaining the thermodynamic activity of each membrane component in phosphatidylcholine (PC)/cholesterol mixtures, that is based upon ESR spin labeling is examined. The thermodynamic activity coefficients, gamma PC and gamma chol, for the PC and cholesterol, respectively, are obtained from the measured orientational order parameters, SPC and S(chol), as a function of cholesterol content for a spin-labeled PC and the sterol-type cholestane spin probe (CSL), respectively, and the effects of water concentration are also considered. At water content of 24 weight%, the thermodynamics of DMPC/cholesterol/water mixtures in the liquid-crystalline state may be treated as a two-component solution ignoring the water, but at lower water content the role of water is important, especially at lower cholesterol concentrations. At lower water content (17 wt%), gamma chol decreases with increasing cholesterol content which implies aggregation. However, at higher water content (24 wt%), gamma chol is found initially to increase as a function of cholesterol content before decreasing at higher cholesterol content. This implies a favorable accommodation for the cholesterol in the membrane at high water and low cholesterol content. Good thermodynamic consistency according to the Gibbs-Duhem equation was obtained for gamma PC and gamma chol at 24 wt% water. The availability of gamma chol (and gamma PC) as a function of cholesterol concentration permits the estimate of the boundary for phase separation. The rotational diffusion coefficients of the labeled PC and of CSL were also obtained from the ESR spectra. A previously proposed universal relation for the perpendicular component of the rotational diffusion tensor, R perpendicular, for CSL in PC/cholesterol mixtures (i.e., R perpendicular = R0 perpendicular exp(-AS2chol/RT)) is confirmed. A change in composition of cholesterol or of water for DMPC/cholesterol/water mixtures affects R perpendicular only through the dependence

  8. An analysis of the quantum effect on the thermodynamic and transport properties of cryogenic hydrogen using molecular dynamics method

    NASA Astrophysics Data System (ADS)

    Nagashima, Hiroki; Tsuda, Shin-ichi; Tsuboi, Nobuyuki; Koshi, Mitsuo; Hayashi, A. Koichi; Tokumasu, Takashi

    2014-03-01

    In this paper, we have analysed an effect of quantum nature of the hydrogen molecule on its thermodynamic and transport properties using molecular dynamics (MD) method based on the path integral method. We performed NVE constant MD simulation and the quantum effect on the molecular mechanism was analysed. The simulation results were compared with experimental data. As a result, we clarified that the quantum nature makes the virial pressure larger than in classical mechanics and taking account the quantum nature makes smaller intermolecular interaction energy and larger repulsive force than classical representation. Besides, we have confirmed that the path-integral-based MD method well reproduces the thermal conductivity and quantum effect on the transport properties is also large.

  9. Effects of pH and ionic strength on the thermodynamics of human serum albumin-photosensitizer binding

    PubMed Central

    Jones, Cecil L.; Dickson, TiReJe; Hayes, Ronald; Thomas, Lana

    2013-01-01

    Fluorescence spectroscopy was used to measure the effects of pH and ionic strength on thermodynamic parameters governing the interaction of human serum albumin with zinc phthalocyanine tetrasulfonic acid. Fluorescence emission of zinc phthalocyanine increases at 686 nm with increasing concentrations of the protein. The non-linear correlation between protein concentration and emission of the photosensitizer was fitted using Chipman’s analysis to calculate the binding affinities. The standard enthalpy and entropy changes were estimated from van’t Hoff analysis of data that were acquired from temperature ramping studies. Results show that reaction is primarily driven by solution dynamics and that the change in enthalpy for the system becomes increasingly unfavorable with increasing pH and ionic strength. The effect of ionic strength on the entropy change for binding is shown to be significantly greater than the effects of pH. The interplay between entropy and enthalpy changes is demonstrated. PMID:24058218

  10. Assessing life's effects on the interior dynamics of planet Earth using non-equilibrium thermodynamics

    NASA Astrophysics Data System (ADS)

    Dyke, J. G.; Gans, F.; Kleidon, A.

    2010-09-01

    Vernadsky described life as the geologic force, while Lovelock noted the role of life in driving the Earth's atmospheric composition to a unique state of thermodynamic disequilibrium. Here, we use these notions in conjunction with thermodynamics to quantify biotic activity as a driving force for geologic processes. Specifically, we explore the hypothesis that biologically-mediated processes operating on the surface of the Earth, such as the biotic enhancement of weathering of continental crust, affect interior processes such as mantle convection and have therefore shaped the evolution of the whole Earth system beyond its surface and atmosphere. We set up three simple models of mantle convection, oceanic crust recycling and continental crust recycling. We describe these models in terms of non-equilibrium thermodynamics in which the generation and dissipation of gradients is central to driving their dynamics and that such dynamics can be affected by their boundary conditions. We use these models to quantify the maximum power that is involved in these processes. The assumption that these processes, given a set of boundary conditions, operate at maximum levels of generation and dissipation of free energy lead to reasonable predictions of core temperature, seafloor spreading rates, and continental crust thickness. With a set of sensitivity simulations we then show how these models interact through the boundary conditions at the mantle-crust and oceanic-continental crust interfaces. These simulations hence support our hypothesis that the depletion of continental crust at the land surface can affect rates of oceanic crust recycling and mantle convection deep within the Earth's interior. We situate this hypothesis within a broader assessment of surface-interior interactions by setting up a work budget of the Earth's interior to compare the maximum power estimates that drive interior processes to the power that is associated with biotic activity. We estimate that the

  11. Nanoscopic Thermodynamics.

    PubMed

    Qi, Weihong

    2016-09-20

    Conventional thermodynamics for bulk substances encounters challenges when one considers materials on the nanometer scale. Quantities such as entropy, enthalpy, free energy, melting temperature, ordering temperature, Debye temperature, and specific heat no longer remain constant but change with the crystal dimension, size, and morphology. Often, one phenomenon is associated with a variety of theories from different perspectives. Still, a model that can reconcile the size and shape dependence of the thermal properties of the nanoscaled substances remains one of the goals of nanoscience and nanotechnology. This Account highlights the nanoscopic thermodynamics for nanoparticles, nanowires, and nanofilms, with particular emphasis on the bond energy model. The central idea is that the atomic cohesive energy determines the thermodynamic performance of a substance and the cohesive energy varies with the atomic coordination environment. It is the cohesive energy difference between the core and the shell that dictates the nanoscopic thermodynamics. This bond energy model rationalizes the following: (i) how the surface dangling bonds depress the melting temperature, entropy, and enthalpy; (ii) how the order-disorder transition of the nanoparticles depends on particle size and how their stability may vary when they are embedded in an appropriate matrix; (iii) predictions of the existence of face-centered cubic structures of Ti, Zr, and Hf at small size; (iv) how two elements that are immiscible in the bulk can form an alloy on the nanoscale, where the critical size can be predicted. The model has enabled us to reproduce the size and shape dependence of a number of physical properties, such as melting temperature, melting entropy, melting enthalpy, ordering temperature, Gibbs free energy, and formation heat, among others, for materials such as Pd, Au, Ag, Cu, Ni, Sn, Pb, In, Bi, Al, Ti, Zr, Hf, In-Al, Ag-Ni, Co-Pt, Cu-Ag, Cu-Ni, Au-Ni, Ag-Pt, and Au-Pt on the nanometer scale

  12. Thermodynamic Analysis of Coherently Grown GaAsN/Ge: Effects of Different Gaseous Sources

    NASA Astrophysics Data System (ADS)

    Kawano, Jun; Kangawa, Yoshihiro; Yayama, Tomoe; Kakimoto, Koichi; Koukitu, Akinori

    2013-04-01

    Thermodynamic analysis of coherently grown GaAs1-xNx on Ge with low N content was performed to determine the relationship between solid composition and growth conditions. In this study, a new algorithm for the simulation code, which is applicable to wider combinations of gaseous sources than the traditional algorithm, was developed to determine the influence of different gaseous sources on N incorporation. Using this code, here we successfully compared two cases: one is a system using trimethylgallium (TMG), AsH3, and NH3, and the other uses dimethylhydrazine (DMHy) instead of NH3. It was found that the optimal N/As ratio of input gas in the system using DMHy was much lower than that using NH3. This shows that the newly developed algorithm could be a useful tool for analyzing the N incorporation during the vapor growth of GaAs1-xNx.

  13. Effects of multi-frequency power ultrasound on the enzymolysis of corn gluten meal: Kinetics and thermodynamics study.

    PubMed

    Jin, Jian; Ma, Haile; Qu, Wenjuan; Wang, Kai; Zhou, Cunshan; He, Ronghai; Luo, Lin; Owusu, John

    2015-11-01

    The effects of multi-frequency power ultrasound (MPU) pretreatment on the kinetics and thermodynamics of corn gluten meal (CGM) were investigated in this research. The apparent constant (KM), apparent break-down rate constant (kA), reaction rate constants (k), energy of activation (Ea), enthalpy of activation (ΔH), entropy of activation (ΔS) and Gibbs free energy of activation (ΔG) were determined by means of the Michaelis-Menten equation, first-order kinetics model, Arrhenius equation and transition state theory, respectively. The results showed that MPU pretreatment can accelerate the enzymolysis of CGM under different enzymolysis conditions, viz. substrate concentration, enzyme concentration, pH, and temperature. Kinetics analysis revealed that MPU pretreatment decreased the KM value by 26.1% and increased the kA value by 7.3%, indicating ultrasound pretreatment increased the affinity between enzyme and substrate. In addition, the values of k for ultrasound pretreatment were increased by 84.8%, 41.9%, 28.9%, and 18.8% at the temperature of 293, 303, 313 and 323 K, respectively. For the thermodynamic parameters, ultrasound decreased Ea, ΔH and ΔS by 23.0%, 24.3% and 25.3%, respectively, but ultrasound had little change in ΔG value in the temperature range of 293-323 K. In conclusion, MPU pretreatment could remarkably enhance the enzymolysis of CGM, and this method can be applied to protein proteolysis industry to produce peptides.

  14. Inclusion of line tension effect in classical nucleation theory for heterogeneous nucleation: A rigorous thermodynamic formulation and some unique conclusions

    SciTech Connect

    Singha, Sanat K.; Das, Prasanta K. Maiti, Biswajit

    2015-03-14

    A rigorous thermodynamic formulation of the geometric model for heterogeneous nucleation including line tension effect is missing till date due to the associated mathematical hurdles. In this work, we develop a novel thermodynamic formulation based on Classical Nucleation Theory (CNT), which is supposed to illustrate a systematic and a more plausible analysis for the heterogeneous nucleation on a planar surface including the line tension effect. The appreciable range of the critical microscopic contact angle (θ{sub c}), obtained from the generalized Young’s equation and the stability analysis, is θ{sub ∞} < θ{sub c} < θ′ for positive line tension and is θ{sub M} < θ{sub c} < θ{sub ∞} for negative line tension. θ{sub ∞} is the macroscopic contact angle, θ′ is the contact angle for which the Helmholtz free energy has the minimum value for the positive line tension, and θ{sub M} is the local minima of the nondimensional line tension effect for the negative line tension. The shape factor f, which is basically the dimensionless critical free energy barrier, becomes higher for lower values of θ{sub ∞} and higher values of θ{sub c} for positive line tension. The combined effect due to the presence of the triple line and the interfacial areas (f{sup L} + f{sup S}) in shape factor is always within (0, 3.2), resulting f in the range of (0, 1.7) for positive line tension. A formerly presumed appreciable range for θ{sub c}(0 < θ{sub c} < θ{sub ∞}) is found not to be true when the effect of negative line tension is considered for CNT. Estimation based on the property values of some real fluids confirms the relevance of the present analysis.

  15. Joint interaction of ethidium bromide and methylene blue with DNA. The effect of ionic strength on binding thermodynamic parameters.

    PubMed

    Vardevanyan, Poghos O; Antonyan, Ara P; Parsadanyan, Marine A; Torosyan, Margarita A; Karapetian, Armen T

    2016-07-01

    Large amount of data of experimental and theoretical studies have shown that ethidium bromide (EtBr) and methylene blue (MB) may bind to nucleic acids via three modes: intercalation between two adjacent base pairs, insertion into the plane between neighboring bases in the same strand (semi-intercalation), and outside binding with negatively charged backbone phosphate groups. The aim of the given research is to examine the behavior of these two ligands at both separate and joint DNA binding. The obtained experimental data show that the effect of simultaneous binding of EtBr and MB on double-stranded DNA has a non-additive effect of separate binding. The analyses of the melting thermodynamic parameters of DNA complexes with two bound ligands suggest competitive mechanism of interaction.

  16. Effects of Salts and Ionic Liquids on the Thermodynamics of Poly(ethylene oxide)-Containing Block Copolymers

    NASA Astrophysics Data System (ADS)

    Wanakule, Nisita; Virgili, Justin; Teran, Alexander; Balsara, Nitash

    2010-03-01

    We explore the thermodynamics of block copolymers doped with the salt, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and the ionic liquid, imidazolium bis(trifluoromethanesulfonyl) imide ([Im][TFSI]). The block copolymers comprise of polyethylene oxide (PEO), a polymer with a higher dielectric constant, and polystyrene (PS), a polymer with a lower dielectric constant. A combination of small-angle x-ray scattering (SAXS) and birefringence was used to determine morphology and order-to-disorder transition temperatures (ODT). Leibler's theory for microphase separation was employed to determine the effective Flory-Huggins interaction parameter. These values are compared to theoretically-determined values of the effective interaction parameter which were calculated with no adjustable parameters using a theory developed by Zhen-Gang Wang.

  17. Anodic Polarization Curves Revisited

    ERIC Educational Resources Information Center

    Liu, Yue; Drew, Michael G. B.; Liu, Ying; Liu, Lin

    2013-01-01

    An experiment published in this "Journal" has been revisited and it is found that the curve pattern of the anodic polarization curve for iron repeats itself successively when the potential scan is repeated. It is surprising that this observation has not been reported previously in the literature because it immediately brings into…

  18. A Hydrostatic Paradox Revisited

    ERIC Educational Resources Information Center

    Ganci, Salvatore

    2012-01-01

    This paper revisits a well-known hydrostatic paradox, observed when turning upside down a glass partially filled with water and covered with a sheet of light material. The phenomenon is studied in its most general form by including the mass of the cover. A historical survey of this experiment shows that a common misunderstanding of the phenomenon…

  19. Parametric Resonance Revisited

    NASA Astrophysics Data System (ADS)

    van den Broeck, C.; Bena, I.

    The phenomenon of parametric resonance is revisited. Several physical examples are reviewed and an exactly solvable model is discussed. A mean field theory is presented for globally coupled parametric oscillators with randomly distributed phases. A new type of collective instability appears, which is similar in nature to that of noise induced phase transitions.

  20. Concept Image Revisited

    ERIC Educational Resources Information Center

    Bingolbali, Erhan; Monaghan, John

    2008-01-01

    Concept image and concept definition is an important construct in mathematics education. Its use, however, has been limited to cognitive studies. This article revisits concept image in the context of research on undergraduate students' understanding of the derivative which regards the context of learning as paramount. The literature, mainly on…

  1. Revisiting Bioaccumulation Criteria

    EPA Science Inventory

    The objective of workgroup 5 was to revisit the B(ioaccumulation) criteria that are currently being used to identify POPs under the Stockholm Convention and PBTs under CEPA, TSCA, REACh and other programs. Despite the lack of a recognized definition for a B substance, we defined ...

  2. The Linguistic Repertoire Revisited

    ERIC Educational Resources Information Center

    Busch, Brigitta

    2012-01-01

    This article argues for the relevance of poststructuralist approaches to the notion of a linguistic repertoire and introduces the notion of language portraits as a basis for empirical study of the way in which speakers conceive and represent their heteroglossic repertoires. The first part of the article revisits Gumperz's notion of a linguistic…

  3. Colloquial Hebrew Imperatives Revisited

    ERIC Educational Resources Information Center

    Bolozky, Shmuel

    2009-01-01

    In revisiting Bolozky's [Bolozky, Shmuel, 1979. "On the new imperative in colloquial Hebrew." "Hebrew Annual Review" 3, 17-24] and Bat-El's [Bat-El, Outi, 2002. "True truncation in colloquial Hebrew imperatives." "Language" 78(4), 651-683] analyses of colloquial Hebrew imperatives, the article argues for restricting Imperative Truncation to the…

  4. Unified first law and the thermodynamics of the apparent horizon in the FRW universe

    SciTech Connect

    Cai Ronggen; Cao Liming

    2007-03-15

    In this paper we revisit the relation between the Friedmann equations and the first law of thermodynamics. We find that the unified first law first proposed by Hayward to treat the outertrapping horizon of a dynamical black hole can be used to the apparent horizon (a kind of inner trapping horizon in the context of the FRW cosmology) of the FRW universe. We discuss three kinds of gravity theorties: Einstein theory, Lovelock thoery, and scalar-tensor theory. In Einstein theory, the first law of thermodynamics is always satisfied on the apparent horizon. In Lovelock theory, treating the higher derivative terms as an effective energy-momentum tensor, we find that this method can give the same entropy formula for the apparent horizon as that of black hole horizon. This implies that the Clausius relation holds for the Lovelock theory. In scalar-tensor gravity, we find, by using the same procedure, the Clausius relation no longer holds. This indicates that the apparent horizon of the FRW universe in the scalar-tensor gravity corresponds to a system of nonequilibrium thermodynamics. We show this point by using the method developed recently by Eling et al. for dealing with the f(R) gravity.

  5. Advances in thermodynamics

    SciTech Connect

    Sieniutycz, S. ); Salamon, P. )

    1990-01-01

    This book covers: nonequilibrium thermodynamics for solar energy applications; finite-time thermodynamics as applied to solar power conversion; thermodynamics and economics; exergy analysis; and an analysis of cumulative exergy consumption and exergy losses.

  6. Effect of Base-Pairing Partner on the Thermodynamic Stability of the Diastereomeric Spiroiminodihydantoin Lesion.

    PubMed

    Gruessner, Brian; Dwarakanath, Megana; Stewart, Elizabeth; Bae, Yoon; Jamieson, Elizabeth R

    2016-03-21

    Oxidation of guanine by reactive oxygen species and high valent metals produces damaging DNA base lesions like 8-oxo-7,8-dihydroguanine (8-oxoG). 8-oxoG can be further oxidized to form the spiroiminodihydantoin (Sp) lesion, which is even more mutagenic. DNA polymerases preferentially incorporate purines opposite the Sp lesion, and DNA glycosylases excise the Sp lesion from the duplex, although the rate of repair is different for the two Sp diastereomers. To further understand the biological processing of the Sp lesion, differential scanning calorimetry studies were performed on a series of 15-mer DNA duplexes. The thermal and thermodynamic stabilities of each of the Sp diastereomers paired to the four standard DNA bases were investigated. It was found that, regardless of the base-pairing partner, the Sp lesion was always highly destabilizing in terms of DNA melting temperature, enthalpic stability, and overall duplex free energy. We found no significant differences between the two Sp diastereomers, but changing the base-pairing partner of the Sp lesion produced slight differences in stability. Specifically, duplexes with Sp:C pairings were always the most destabilized, whereas pairing the Sp lesion with a purine base modestly increased stability. Overall, these results suggest that, although the stability of the Sp diastereomers cannot explain the differences in the rates of repair by DNA glycosylases, the most stable base-pairing partners do correspond with the nucleotide preference of DNA polymerases.

  7. Classical and quantum many-body effects on the critical properties and thermodynamic regularities of silicon

    NASA Astrophysics Data System (ADS)

    Desgranges, C.; Anderson, P. W.; Delhommelle, J.

    2017-02-01

    Using molecular simulation, we determine the critical properties of Si as well as the loci for several remarkable thermodynamic contours spanning the supercritical region of the phase diagram. We consider a classical three-body potential as well as a quantum (tight-binding) many-body model, and determine the loci for the ideality contours, including the Zeno line and the H line of ideal enthalpy. The two strategies (classical or quantum) lead to strongly asymmetric binodals and to critical properties in good agreement with each other. The Zeno and H lines are found to remain linear over a wide temperature interval, despite the changes in electronic structure undergone by the fluid along these contours. We also show that the classical and quantum model yield markedly different results for the parameters defining the H line, the exponents for the power-laws underlying the line of minima for the isothermal enthalpy and for the density required to achieve ideal behavior, most notably for the enthalpy.

  8. Effects of solution composition on the theoretical prediction of ice nucleation kinetics and thermodynamics.

    PubMed

    Karlsson, Jens O M

    2010-02-01

    Predictions by various mathematical models of intracellular ice formation (proposed by Mazur, Pitt, Toner, and Karlsson, respectively) were compared to the known thermodynamic and kinetic behavior of ice formation in supercooled aqueous systems. The older models (Mazur, Pitt, and Toner) significantly underestimated the magnitude of colligative nonequilibrium freezing point depression in response to increased concentration of solutes, such as salts or cryoprotectants. Furthermore, kinetics predicted using phenomenological models (by Mazur and Pitt) exhibited implausible temperature-dependence, with the probability of intracellular ice formation being allowed to increase even at temperatures below the glass transition point. The Toner model, on the other hand, produced invalid results at temperatures below -48 degrees C. The Karlsson model was the only model that consistently yielded realistic predictions over a wide range of temperatures and solute concentrations, especially in the presence of cryoprotectant additives. To facilitate adoption of the Karlsson model of intracellular ice nucleation, the complete set of model equations has been collected and described in detail.

  9. Classical and quantum many-body effects on the critical properties and thermodynamic regularities of silicon.

    PubMed

    Desgranges, C; Anderson, P W; Delhommelle, J

    2017-02-01

    Using molecular simulation, we determine the critical properties of Si as well as the loci for several remarkable thermodynamic contours spanning the supercritical region of the phase diagram. We consider a classical three-body potential as well as a quantum (tight-binding) many-body model, and determine the loci for the ideality contours, including the Zeno line and the H line of ideal enthalpy. The two strategies (classical or quantum) lead to strongly asymmetric binodals and to critical properties in good agreement with each other. The Zeno and H lines are found to remain linear over a wide temperature interval, despite the changes in electronic structure undergone by the fluid along these contours. We also show that the classical and quantum model yield markedly different results for the parameters defining the H line, the exponents for the power-laws underlying the line of minima for the isothermal enthalpy and for the density required to achieve ideal behavior, most notably for the enthalpy.

  10. Influence of Response-Effect Feedback on Learning and Performance of a Complex Key-Pressing Task: Morin and Grant (1955) Revisited.

    PubMed

    Chen, Jing; Proctor, Robert W

    2015-01-01

    Response effects, also called action effects, are events produced as a consequence of a response. Morin and Grant (1955) conducted an 8-choice task in which, when one of the response keys was pressed, a feedback light (i.e., response effect) was lit in a row below the stimulus lights. Across participants, stimulus-response and response-effect mappings varied in compatibility, ranging from perfectly corresponding, to random, to perfectly mirror-reversed mapping. After several practice sessions, the feedback lights were removed in a transfer session, and response times increased greatly, particularly for the mappings without much structure, indicating reliance on the feedback during practice. We revisited this paradigm by means of 2 experiments that examined the influence on acquisition and transfer performance of task instruction, reliability of the visual feedback, and task difficulty. Lower task difficulty and unreliable visual feedback resulted in superior performance in the transfer session, indicating better learning of the stimulus-response mapping and less reliance on the feedback during learning. Task instructions that emphasized learning of the mapping or indicated that there would be a later test without the feedback lights did not influence participants' performance in the transfer session. These findings are discussed in relation to several of Healy and colleagues' principles of skill acquisition and transfer and in the context of contemporary research on response-effect associations.

  11. Effects of a finite number of particles on the thermodynamic properties of a harmonically trapped ideal charged Bose gas in a constant magnetic field

    NASA Astrophysics Data System (ADS)

    Duan-Liang, Xiao; Meng-Yun, Lai; Xiao-Yin, Pan

    2016-01-01

    We investigate the thermodynamic properties of an ideal charged Bose gas confined in an anisotropic harmonic potential and a constant magnetic field. Using an accurate density of states, we calculate analytically the thermodynamic potential and consequently various intriguing thermodynamic properties, including the Bose-Einstein transition temperature, the specific heat, magnetization, and the corrections to these quantities due to the finite number of particles are also given explicitly. In contrast to the infinite number of particles scenarios, we show that those thermodynamic properties, particularly the Bose-Einstein transition temperature depends upon the strength of the magnetic field due to the finiteness of the particle numbers, and the collective effects of a finite number of particles become larger when the particle number decreases. Moreover, the magnetization varies with the temperature due to the finiteness of the particle number while it keeps invariant in the thermodynamic limit N → ∞. Project supported by the National Natural Science Foundation of China (Grant No. 11375090), and the K. C. Wong Magna Foundation of Ningbo University, China.

  12. Effect of base modifications on structure, thermodynamic stability, and gene silencing activity of short interfering RNA

    PubMed Central

    Sipa, Katarzyna; Sochacka, Elzbieta; Kazmierczak-Baranska, Julia; Maszewska, Maria; Janicka, Magdalena; Nowak, Genowefa; Nawrot, Barbara

    2007-01-01

    A series of nucleobase-modified siRNA duplexes containing “rare” nucleosides, 2-thiouridine (s2U), pseudouridine (Ψ), and dihydrouridine (D), were evaluated for their thermodynamic stability and gene silencing activity. The duplexes with modified units at terminal positions exhibited similar stability as the nonmodified reference. Introduction of the s2U or Ψ units into the central part of the antisense strand resulted in duplexes with higher melting temperatures (Tm). In contrary, D unit similarly like wobble base pair led to the less stable duplexes (ΔTm 3.9 and 6.6°C, respectively). Gene-silencing activity of siRNA duplexes directed toward enhanced green fluorescent protein or beta-site APP cleaving enzyme was tested in a dual fluorescence assay. The duplexes with s2U and Ψ units at their 3′-ends and with a D unit at their 5′-ends (with respect to the guide strands) were the most potent gene expression inhibitors. Duplexes with s2U and Ψ units at their 5′-ends were by 50% less active than the nonmodified counterpart. Those containing a D unit or wobble base pair in the central domain had the lowest Tm, disturbed the A-type helical structure, and had more than three times lower activity than their nonmodified congener. Activity of siRNA containing the wobble base pair could be rescued by placing the thio-nucleoside at the position 3′-adjacent to the mutation site. Thermally stable siRNA molecules containing several s2U units in the antisense strand were biologically as potent as their native counterparts. The present results provide a new chemical tool for modulation of siRNA gene-silencing activity. PMID:17585051

  13. Effect of Water Content in N-Methylmorpholine N-Oxide/Cellulose Solutions on Thermodynamics, Structure, and Hydrogen Bonding.

    PubMed

    Rabideau, Brooks D; Ismail, Ahmed E

    2015-12-03

    Native crystalline cellulose is notoriously difficult to dissolve due to its dense hydrogen bond network between chains and weaker hydrophobic forces between cellulose sheets. N-Methylmorpholine N-oxide (NMMO), the solvent behind the Lyocell process, is one of the most successful commercial solvents for the nonderivatized dissolution of cellulose. In this process, water plays a very important role. Its presence at low concentrations allows NMMO to dissolve substantial amounts of cellulose, while at much higher concentrations it precipitates the crystalline fibers. Using all-atom molecular dynamics, we study the thermodynamic and structural properties of ternary solutions of cellulose, NMMO, and water. Using the two-phase thermodynamic method to calculate solvent entropy, we estimate the free energy of dissolution of cellulose as a function of the water concentration and find a transition of spontaneity that is in excellent agreement with experiment. In pure water, we find that cellulose dissolution is nonspontaneous, a result that is due entirely to strong decreases in water entropy. Although the combined effect of enthalpy on dissolution in water is negligible, we observe a net loss of hydrogen bonds, resulting in a change in hydrogen bond energy that opposes dissolution. At lower water concentrations, cellulose dissolution is spontaneous and largely driven by decreases in enthalpy, with solvent entropy playing only a very minor role. When searching for the root causes of this enthalpy decrease, a complex picture emerges in which not one but many different factors contribute to NMMO's good solvent behavior. The reduction in enthalpy is led by the formation of strong hydrogen bonds between cellulose and NMMO's N-oxide, intensified through van der Waals interactions between NMMO's nonpolar body and the nonpolar surfaces of cellulose and unhindered by water at low concentrations due to the formation of efficient hydrogen bonds between water and cellulose.

  14. Kinetic and thermodynamic analysis of the inhibitory effects of maltose, glucose, and related carbohydrates on wheat β-amylase.

    PubMed

    Daba, Tadessa; Kojima, Kenji; Inouye, Kuniyo

    2013-04-10

    Inhibition of wheat β-amylase (WBA) by glucose and maltose was studied by kinetics and thermodynamics. The inhibitory effects of fructose, difructose, sucrose, trehalose, cellobiose, acarbose, and 1-deoxynojirimycin on WBA were also evaluated. The half maximal inhibitory concentrations (IC50) of acarbose, maltose and glucose were 0.06±0.01M, 0.22±0.09M, and 1.41±0.17M, respectively. The inhibitor constant (Ki) and the thermodynamic parameters such as changes in Gibbs energy (ΔG), enthalpy (ΔH), and entropy (ΔS) of the dissociation reactions of the WBA-glucose and WBA-maltose complexes were temperature and pH-dependent. The dissociation reactions were endothermic and enthalpy-driven. Both glucose and maltose behaved as competitive inhibitors at pH 3.0 and 5.4 at a temperature of 25°C with respective Ki values of 0.33±0.02M and 0.12±0.03M. In contrast, both sugars exhibited uncompetitive inhibition at pH 9 at a temperature of 25°C with Ki values of 0.21±0.03M for glucose and 0.11±0.04M for maltose. The pH-dependence of the inhibition type and Ki values indicate that the ionizing groups of WBA influence drastically the interaction with these carbohydrates. This evidence enables us to consider temperature and pH in the WBA-catalyzed hydrolysis to manipulate the inhibition by end-product, maltose, and even by glucose.

  15. Thermodynamic studies on the solvent effects in chromatography on molecularly imprinted polymers

    SciTech Connect

    Kim, Hyunjung; Guiochon, Georges A

    2005-03-01

    Molecularly imprinted polymers (MIPs) are used as highly enantioselective stationary phases in liquid chromatography. To optimize the binding performance of MIPs, different types of polar modifiers are frequently used. Previous studies have shown that the hydrogen-bonding donor parameter (HBD) of the modifier has a large influence on the binding performance of MIPs in chiral separations. This possibility is addressed in a detailed thermodynamic study of a Fmoc-l-tryptophan (Fmoc-l-Trp) imprinted polymer, eluted with four different polar modifiers, i.e., THF, propan-2-ol, methanol, and acetic acid, which have different HBDs (0.00, 0.33, 0.43, and 0.61, respectively). Adsorption isotherm data for each enantiomer in each of these organic modifiers were acquired by frontal analysis over a 20000 dynamic concentration range. Nonlinear regression of the isotherm data, along with independent calculation of the affinity energy distributions, identified four different types of binding sites coexisting for the enantiomers on the MIP. The exception was acetic acid, which has the highest HBD. In this case, three types of binding sites only coexist on the MIP. The isotherm parameters obtained from these data show the following: (1) The association energies of the two enantiomers with a given type of sites have a similar magnitude; however, the density of the sites is higher for the template than for its antipode. (2) The nature of the organic modifier has a larger influence on the density of high-energy sites than on the association constant of these sites. (3) The molecular size of the organic modifier has a larger influence on the site density (especially for Fmoc-d-Trp) than does HBD. (4) Using an organic modifier with a higher HBD reduces the enantioselectivity on each site. (5) High-energy sites are more enantioselective than low-energy ones. (6) Using an organic modifier with a high HBD causes a larger reduction in the density of high-energy sites approached by the

  16. Actinide Partitioning and Radiation Effects in U(VI)-Solids: Thermodynamic & Mechanistic Study

    SciTech Connect

    Clark, Sue B.; Ewing, Rodney C.

    2010-05-20

    correlations between our measured adsorption constants and published thermodynamic values for their behavior in aqueous systems to develop relevant LFERs for these systems. Such LFERs can now be used to predict non-U actinide adsorption to assemblages of U(VI) solid phases. We also investigated the impact of ballistic interactions from ionizing radiation and subsequent annealing on the overall partitioning of the non-U actinides to the U(VI) solids.

  17. The effects of organic solvents on the folding pathway and associated thermodynamics of proteins: a microscopic view.

    PubMed

    Yu, Yuqi; Wang, Jinan; Shao, Qiang; Shi, Jiye; Zhu, Weiliang

    2016-01-18

    Protein folding is subject to the effects of solvation environment. A variety of organic solvents are used as additives for in vitro refolding of denatured proteins. Examination of the solvent effects on protein folding could be of fundamental importance to understand the molecular interactions in determining protein structure. This article investigated the folding of α-helix and β-hairpin structures in water and the solutions of two representative refolding additives (methanol (MeOH) and 1-Ethyl-3-methylimidazolium chloride (EMIM-Cl) ionic liquid) using REMD simulations. For both α-helix and β-hairpin in MeOH/water solution or α-helix in EMIM-Cl/water solution, the transient structures along the folding pathway are consistent with the counterparts in water but the relative statistical weights are changed, leading to the decrease in the overall folding free energy barrier. Accordingly, MeOH promotes the folding of both α-helix and β-hairpin but EMIM-Cl ionic liquid only promotes the folding of α-helix, consistent with experimental observations. The present study reveals for the first time the trivial effects on folding route but significant effects on folding thermodynamics from MeOH and EMIM-Cl, explaining the function of protein refolding additives and testifying the validity of the folding mechanism revealed by in vitro protein folding study using refolding additives.

  18. Thermodynamics of Radiation Modes

    ERIC Educational Resources Information Center

    Pina, Eduardo; de la Selva, Sara Maria Teresa

    2010-01-01

    We study the equilibrium thermodynamics of the electromagnetic radiation in a cavity of a given volume and temperature. We found three levels of description, the thermodynamics of one mode, the thermodynamics of the distribution of frequencies in a band by summing over the frequencies in it and the global thermodynamics by summing over all the…

  19. Revisiting Dialogues and Monologues

    ERIC Educational Resources Information Center

    Kvernbekk, Tone

    2012-01-01

    In educational discourse dialogue tends to be viewed as being (morally) superior to monologue. When we look at them as basic forms of communication, we find that dialogue is a two-way, one-to-one form and monologue is a one-way, one-to-many form. In this paper I revisit the alleged (moral) superiority of dialogue. First, I problematize certain…

  20. Clinical ethics revisited

    PubMed Central

    Singer, Peter A; Pellegrino, Edmund D; Siegler, Mark

    2001-01-01

    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. PMID:11346456

  1. Mountain Rivers Revisited

    NASA Astrophysics Data System (ADS)

    Schultz, Colin

    2011-12-01

    Published in 2000, the original Mountain Rivers was written to provide a concise summary of the scientific understanding of the distinct subset of rivers that gave the book its name. Spurred by developments in the field in the past decade, the book's author, Ellen Wohl, produced Mountain Rivers Revisited, an updated edition aimed at graduate students and professional researchers. In this interview, Eos talks to Wohl about steep channels, climate change, and opportunities for future research.

  2. Thermodynamics of Protein–Protein Interactions of cMyc, Max, and Mad: Effect of Polyions on Protein Dimerization†

    PubMed Central

    Banerjee, Anamika; Hu, Jianzhong; Goss, Dixie J.

    2010-01-01

    The Myc–Max–Mad network of proteins activates or represses gene transcription depending on whether the dimerization partner of Max is c-Myc or Mad. To elucidate the physical properties of these protein–protein interactions, fluorescence anisotropy of TRITC-labeled Max was used. The binding affinities and thermodynamics of dimerization of the Max–Max homodimer and c-Myc–Max and Mad–Max heterodimers were determined. Our results indicate that c-Myc and Max form the most stable heterodimer. Previous work [Kohler, J. J., Metallo, S. J., Schneider, T. L., and Schepartz, A. (1999) Proc. Natl. Acad. Sci. U.S.A. 96, 11735–9] has shown that instead of dimerizing first and then binding to DNA, these proteins use a monomer pathway in which a monomer binds to DNA followed by dimerization on the surface of the DNA. The DNA E-box affects the dimerization, but nonspecific effects may also play a role. The influence of polyions, poly-l-lysine and poly-l-glutamic acid, were investigated to determine the effects of charged polymers other than DNA on homodimerization and heterodimerization. While the positively charged poly-l-lysine, PLL, did not show any significant effect, negatively charged poly-l-glutamic acid, PLG, stabilized both heterodimers and homodimers by 2–3 kJ/mol. These data suggest that in the cell nucleus the presence of negatively charged DNA or RNA could nonspecifically aid in association of these proteins. Calculations of ΔH° and ΔS° from the temperature dependence of Kd indicated that although the thermodynamic parameters for the dimer are different, the reactions for all three dimers are driven by negative (favorable) enthalpic and negative (unfavorable) entropic contributions. In the presence of PLG, entropy became more negative with the effect being largest for c-Myc–Max heterodimers. This suggests that van der Waals and H-bonding interactions are predominant in dimerization of these proteins. PMID:16475822

  3. Enceladus' tidal dissipation revisited

    NASA Astrophysics Data System (ADS)

    Tobie, Gabriel; Behounkova, Marie; Choblet, Gael; Cadek, Ondrej; Soucek, Ondrej

    2016-10-01

    A series of chemical and physical evidence indicates that the intense activity at Enceladus' South Pole is related to a subsurface salty water reservoir underneath the tectonically active ice shell. The detection of a significant libration implies that this water reservoir is global and that the average ice shell thickness is about 20-25km (Thomas et al. 2016). The interpretation of gravity and topography data further predicts large variations in ice shell thickness, resulting in a shell potentially thinner than 5 km in the South Polar Terrain (SPT) (Cadek et al. 2016). Such an ice shell structure requires a very strong heat source in the interior, with a focusing mechanism at the SPT. Thermal diffusion through the ice shell implies that at least 25-30 GW is lost into space by passive diffusion, implying a very efficient dissipation mechanism in Enceladus' interior to maintain such an ocean/ice configuration thermally stable.In order to determine in which conditions such a large dissipation power may be generated, we model the tidal response of Enceladus including variable ice shell thickness. For the rock core, we consider a wide range of rheological parameters representative of water-saturated porous rock materials. We demonstrate that the thinning toward the South Pole leads to a strong increase in heat production in the ice shell, with a optimal thickness obtained between 1.5 and 3 km, depending on the assumed ice viscosity. Our results imply that the heat production in the ice shell within the SPT may be sufficient to counterbalance the heat loss by diffusion and to power eruption activity. However, outside the SPT, a strong dissipation in the porous core is required to counterbalance the diffusive heat loss. We show that about 20 GW can be generated in the core, for an effective viscosity of 1012 Pa.s, which is comparable to the effective viscosity estimated in water-saturated glacial tills on Earth. We will discuss the implications of this revisited tidal

  4. Water in Basaltic Melts: an Experimental and Thermodynamic Study of the Effect of H2O on Liquidus Temperatures.

    NASA Astrophysics Data System (ADS)

    Medard, E.; Grove, T. L.

    2006-12-01

    We present a thermodynamic model for the influence of H2O on liquidus temperatures of olivine-saturated primitive basaltic and andesitic melts. The thermodynamic model has been fitted to a suite of H2O-saturated liquidus experiments carried out on a primitive high-alumina basalt from Medicine Lake Volcano (82-72f) over a pressure range of 10 to 1000 MPa. The model of Silver and Stolper (S+S, 1985, J.Geol. 93:161) has been applied to the experimental data. This model uses the assumption of simple ideal mixing between water species and the anionic matrix in the melt. Water in the melt dissolves as molecular H2O, or dissociates to hydroxyl groups and an oxygen atomic network. For 82-72f, the liquidus olivine shows little compositional variability (Fo87.4 to Fo88.4) over the broad range of pressures and temperatures investigated that is not correlated with H2O content of the melt. This observation supports our assumption that major effect of H2O is on the anionic species in the melt and not on the cation equilibria (e.g. Mg and Si). The model reproduces the experimental data well. We find that there is a large influence of H2O addition on melting point for small amounts of H2O, resulting in a concave-down curvature when liquidus depression is plotted against the amount of H2O added. For addition of 0.8 and 5 wt% H2O to 82-72f, the liquidus is depressed by 35 K and 130 K, respectively. The best fits are obtained by assuming partial water dissociation to OH and H2O species, using the equilibrium constant measured by Stolper (1982). S+S applied their model to simple systems (diopside/H2O, albite/H2O, silica/H2O), and recovered the melting behavior extremely well. They also suggested that melt structure/composition influences the amount of liquidus depression caused by H2O addition. We have investigated the influence of bulk composition by performing complementary experiments on a high-magnesian andesite from Mount Shasta, and on a K, Na, and P rich alkali basalt from

  5. Dynamic Topography Revisited

    NASA Astrophysics Data System (ADS)

    Moresi, Louis

    2015-04-01

    Dynamic Topography Revisited Dynamic topography is usually considered to be one of the trinity of contributing causes to the Earth's non-hydrostatic topography along with the long-term elastic strength of the lithosphere and isostatic responses to density anomalies within the lithosphere. Dynamic topography, thought of this way, is what is left over when other sources of support have been eliminated. An alternate and explicit definition of dynamic topography is that deflection of the surface which is attributable to creeping viscous flow. The problem with the first definition of dynamic topography is 1) that the lithosphere is almost certainly a visco-elastic / brittle layer with no absolute boundary between flowing and static regions, and 2) the lithosphere is, a thermal / compositional boundary layer in which some buoyancy is attributable to immutable, intrinsic density variations and some is due to thermal anomalies which are coupled to the flow. In each case, it is difficult to draw a sharp line between each contribution to the overall topography. The second definition of dynamic topography does seem cleaner / more precise but it suffers from the problem that it is not measurable in practice. On the other hand, this approach has resulted in a rich literature concerning the analysis of large scale geoid and topography and the relation to buoyancy and mechanical properties of the Earth [e.g. refs 1,2,3] In convection models with viscous, elastic, brittle rheology and compositional buoyancy, however, it is possible to examine how the surface topography (and geoid) are supported and how different ways of interpreting the "observable" fields introduce different biases. This is what we will do. References (a.k.a. homework) [1] Hager, B. H., R. W. Clayton, M. A. Richards, R. P. Comer, and A. M. Dziewonski (1985), Lower mantle heterogeneity, dynamic topography and the geoid, Nature, 313(6003), 541-545, doi:10.1038/313541a0. [2] Parsons, B., and S. Daly (1983), The

  6. NON-LOCAL THERMODYNAMICAL EQUILIBRIUM EFFECTS ON THE IRON ABUNDANCE OF ASYMPTOTIC GIANT BRANCH STARS IN 47 TUCANAE

    SciTech Connect

    Lapenna, E.; Mucciarelli, A.; Lanzoni, B.; Ferraro, F. R.; Dalessandro, E.; Massari, D.

    2014-12-20

    We present the iron abundance of 24 asymptotic giant branch (AGB) stars, members of the globular cluster 47 Tucanae, obtained with high-resolution spectra collected with the FEROS spectrograph at the MPG/ESO 2.2 m Telescope. We find that the iron abundances derived from neutral lines (with a mean value [Fe I/H] =–0.94 ± 0.01, σ = 0.08 dex) are systematically lower than those derived from single ionized lines ([Fe II/H] =–0.83 ± 0.01, σ = 0.05 dex). Only the latter are in agreement with those obtained for a sample of red giant branch (RGB) cluster stars, for which the Fe I and Fe II lines provide the same iron abundance. This finding suggests that non-local thermodynamical equilibrium (NLTE) effects driven by overionization mechanisms are present in the atmosphere of AGB stars and significantly affect the Fe I lines while leaving Fe II features unaltered. On the other hand, the very good ionization equilibrium found for RGB stars indicates that these NLTE effects may depend on the evolutionary stage. We discuss the impact of this finding on both the chemical analysis of AGB stars and on the search for evolved blue stragglers.

  7. Effect of Backbone Design on Hybridization Thermodynamics of Oligo-nucleic Acids: A Coarse-Grained Molecular Dynamics Simulation Study

    NASA Astrophysics Data System (ADS)

    Ghobadi, Ahmadreza F.; Jayaraman, Arthi

    DNA hybridization is the basis of various bio-nano technologies, such as DNA origami and assembly of DNA-functionalized nanoparticles. A hybridized double stranded (ds) DNA is formed when complementary nucleobases on hybridizing strands exhibit specific and directional hydrogen bonds through canonical Watson-Crick base-pairing interactions. In recent years, the need for cheaper alternatives and significant synthetic advances have driven design of DNA mimics with new backbone chemistries. However, a fundamental understanding of how these backbone modifications in the oligo-nucleic acids impact the hybridization and melting behavior of the duplex is still lacking. In this talk, we present our recent findings on impact of varying backbone chemistry on hybridization of oligo-nucleic acid duplexes. We use coarse-grained molecular dynamics simulations to isolate the effect of strand flexibility, electrostatic interactions and nucleobase spacing on the melting curves for duplexes with various strand sequences and concentrations. Since conjugation of oligo-nucleic acids with polymers serve as building blocks for thermo-responsive polymer networks and gels, we also present the effect of such conjugation on hybridization thermodynamics and polymer conformation.

  8. Numerical investigation and thermodynamic analysis of the effect of electrolyte flow rate on performance of all vanadium redox flow batteries

    NASA Astrophysics Data System (ADS)

    Khazaeli, Ali; Vatani, Ali; Tahouni, Nassim; Panjeshahi, Mohammad Hassan

    2015-10-01

    In flow batteries, electrolyte flow rate plays a crucial role on the minimizing mass transfer polarization which is at the compensation of higher pressure drop. In this work, a two-dimensional numerical method is applied to investigate the effect of electrolyte flow rate on cell voltage, maximum depth of discharge and pressure drop a six-cell stack of VRFB. The results show that during the discharge process, increasing electrolyte flow rate can raise the voltage of each cell up to 50 mV on average. Moreover, the maximum depth of discharge dramatically increases with electrolyte flow rate. On the other hand, the pressure drop also positively correlates with electrolyte flow rate. In order to investigate all these effects simultaneously, average energy and exergy efficiencies are introduced in this study for the transient process of VRFB. These efficiencies give insight into choosing an appropriate strategy for the electrolyte flow rate. Finally, the energy efficiency of electricity storage using VRFB is investigated and compared with other energy storage systems. The results illustrate that this kind of battery has at least 61% storage efficiency based on the second law of thermodynamics, which is considerably higher than that of their counterparts.

  9. Nonequilibrium thermodynamics of nucleation

    SciTech Connect

    Schweizer, M.; Sagis, L. M. C.

    2014-12-14

    We present a novel approach to nucleation processes based on the GENERIC framework (general equation for the nonequilibrium reversible-irreversible coupling). Solely based on the GENERIC structure of time-evolution equations and thermodynamic consistency arguments of exchange processes between a metastable phase and a nucleating phase, we derive the fundamental dynamics for this phenomenon, based on continuous Fokker-Planck equations. We are readily able to treat non-isothermal nucleation even when the nucleating cores cannot be attributed intensive thermodynamic properties. In addition, we capture the dynamics of the time-dependent metastable phase being continuously expelled from the nucleating phase, and keep rigorous track of the volume corrections to the dynamics. Within our framework the definition of a thermodynamic nuclei temperature is manifest. For the special case of nucleation of a gas phase towards its vapor-liquid coexistence, we illustrate that our approach is capable of reproducing recent literature results obtained by more microscopic considerations for the suppression of the nucleation rate due to nonisothermal effects.

  10. Nonequilibrium thermodynamics of nucleation.

    PubMed

    Schweizer, M; Sagis, L M C

    2014-12-14

    We present a novel approach to nucleation processes based on the GENERIC framework (general equation for the nonequilibrium reversible-irreversible coupling). Solely based on the GENERIC structure of time-evolution equations and thermodynamic consistency arguments of exchange processes between a metastable phase and a nucleating phase, we derive the fundamental dynamics for this phenomenon, based on continuous Fokker-Planck equations. We are readily able to treat non-isothermal nucleation even when the nucleating cores cannot be attributed intensive thermodynamic properties. In addition, we capture the dynamics of the time-dependent metastable phase being continuously expelled from the nucleating phase, and keep rigorous track of the volume corrections to the dynamics. Within our framework the definition of a thermodynamic nuclei temperature is manifest. For the special case of nucleation of a gas phase towards its vapor-liquid coexistence, we illustrate that our approach is capable of reproducing recent literature results obtained by more microscopic considerations for the suppression of the nucleation rate due to nonisothermal effects.

  11. Nonequilibrium thermodynamics of nucleation

    NASA Astrophysics Data System (ADS)

    Schweizer, M.; Sagis, L. M. C.

    2014-12-01

    We present a novel approach to nucleation processes based on the GENERIC framework (general equation for the nonequilibrium reversible-irreversible coupling). Solely based on the GENERIC structure of time-evolution equations and thermodynamic consistency arguments of exchange processes between a metastable phase and a nucleating phase, we derive the fundamental dynamics for this phenomenon, based on continuous Fokker-Planck equations. We are readily able to treat non-isothermal nucleation even when the nucleating cores cannot be attributed intensive thermodynamic properties. In addition, we capture the dynamics of the time-dependent metastable phase being continuously expelled from the nucleating phase, and keep rigorous track of the volume corrections to the dynamics. Within our framework the definition of a thermodynamic nuclei temperature is manifest. For the special case of nucleation of a gas phase towards its vapor-liquid coexistence, we illustrate that our approach is capable of reproducing recent literature results obtained by more microscopic considerations for the suppression of the nucleation rate due to nonisothermal effects.

  12. The Effect of Temperature on the Enzyme-Catalyzed Reaction: Insights from Thermodynamics

    ERIC Educational Resources Information Center

    Aledo, Juan Carlos; Jimenez-Riveres, Susana; Tena, Manuel

    2010-01-01

    When teaching the effect of temperature on biochemical reactions, the problem is usually oversimplified by confining the thermal effect to the catalytic constant, which is identified with the rate constant of the elementary limiting step. Therefore, only positive values for activation energies and values greater than 1 for temperature coefficients…

  13. Effect of the revisit interval and temporal upscaling methods on the accuracy of remotely sensed evapotranspiration estimates

    NASA Astrophysics Data System (ADS)

    Alfieri, Joseph G.; Anderson, Martha C.; Kustas, William P.; Cammalleri, Carmelo

    2017-01-01

    Accurate spatially distributed estimates of actual evapotranspiration (ET) derived from remotely sensed data are critical to a broad range of practical and operational applications. However, due to lengthy return intervals and cloud cover, data acquisition is not continuous over time, particularly for satellite sensors operating at medium ( ˜ 100 m) or finer resolutions. To fill the data gaps between clear-sky data acquisitions, interpolation methods that take advantage of the relationship between ET and other environmental properties that can be continuously monitored are often used. This study sought to evaluate the accuracy of this approach, which is commonly referred to as temporal upscaling, as a function of satellite revisit interval. Using data collected at 20 Ameriflux sites distributed throughout the contiguous United States and representing four distinct land cover types (cropland, grassland, forest, and open-canopy) as a proxy for perfect retrievals on satellite overpass dates, this study assesses daily ET estimates derived using five different reference quantities (incident solar radiation, net radiation, available energy, reference ET, and equilibrium latent heat flux) and three different interpolation methods (linear, cubic spline, and Hermite spline). Not only did the analyses find that the temporal autocorrelation, i.e., persistence, of all of the reference quantities was short, it also found that those land cover types with the greatest ET exhibited the least persistence. This carries over to the error associated with both the various scaled quantities and flux estimates. In terms of both the root mean square error (RMSE) and mean absolute error (MAE), the errors increased rapidly with increasing return interval following a logarithmic relationship. Again, those land cover types with the greatest ET showed the largest errors. Moreover, using a threshold of 20 % relative error, this study indicates that a return interval of no more than 5 days is

  14. Thermodynamic modelling of a double-effect LiBr-H2O absorption refrigeration cycle

    NASA Astrophysics Data System (ADS)

    Iranmanesh, A.; Mehrabian, M. A.

    2012-12-01

    The goal of this paper is to estimate the conductance of components required to achieve the approach temperatures, and gain insights into a double-effect absorption chiller using LiBr-H2O solution as the working fluid. An in-house computer program is developed to simulate the cycle. Conductance of all components is evaluated based on the approach temperatures assumed as input parameters. The effect of input data on the cycle performance and the exergetic efficiency are investigated.

  15. Nylon 6 electrospun nanofibers mat as effective sorbent for the removal of estrogens: kinetic and thermodynamic studies

    NASA Astrophysics Data System (ADS)

    Qi, Fei-Fei; Cao, Yang; Wang, Min; Rong, Fei; Xu, Qian

    2014-07-01

    Nylon 6 electrospun nanofibers mat was prepared via electrospinning for the removal of three estrogens, namely, diethylstilbestrol (DES), dienestrol (DS), and hexestrol (HEX) from aqueous solution. Static adsorption as well as the dynamic adsorption was evaluated by means of batch and dynamic disk flow mode, respectively. The kinetic study indicated that the adsorption of the target compounds could be well fitted by the pseudo-second-order equation, suggesting the intra-particle/membrane diffusion process as the rate-limiting step of the adsorption process. The adsorption equilibrium data were all fitted well to the Freundlich isotherm models, with a maximum adsorption capacity values in the range of 97.71 to 208.95 mg/g, which can be compared to or moderately higher than other sorbents published in the literatures. The dynamic disk mode studies indicated that the mean removal yields of three model estrogens were over 95% with a notable smaller amount of adsorbent (4 mg). Thermodynamic study revealed that the adsorption process was exothermic and spontaneous in nature. Desorption results showed that the adsorption capacity can remain up to 80% after seven times usage. It was suggested that Nylon 6 electrospun nanofibers mat has great potential as a novel effective sorbent material for estrogens removal.

  16. Cloud thermodynamic phase, cirrus cloud optical thickness and effective diameter in the Version 6 Atmospheric Infrared Sounder data release

    NASA Astrophysics Data System (ADS)

    Kahn, B. H.; Irion, F. W.; Manning, E. M.; Oliphant, R.; Schreier, M. M.; Yue, Q.; Fetzer, E.; Jin, H.; Nasiri, S. L.; Baum, B. A.; Ou, S. S.; Takano, Y.; Liou, K.

    2011-12-01

    The development of a new set of cloud products produced in the upcoming Version 6 release of the Atmospheric Infrared Sounder (AIRS) algorithm is described and initial results are presented. The three new cloud retrieval products include (1) cloud thermodynamic phase, (2) cirrus cloud optical thickness, and (3) cirrus cloud effective diameter. The retrieval methodology of the cirrus cloud parameters is based on an optimal estimation approach that uses Level 1B observed radiances and Level 2 cloud clearing-derived atmospheric profiles that define the atmospheric state, surface temperature and emissivity, and cloud top temperature. The Stand Alone AIRS Radiative Transfer Algorithm (SARTA) is coupled to a delta-4-stream (D4S) approximation (SARTA+D4S) to simulate single-layered cloudy spectra. The same ice scattering models used in the Moderate Resolution Imaging Spectroradiometer (MODIS) Collection 5 release are also used in the SARTA+D4S model. The error characterization and averaging kernels associated with the retrieved fields, and various challenges to operational implementation, will be highlighted. Statistical comparisons are made to pixel-scale collocated Aqua MODIS retrievals, with similarities and differences quantified in the AIRS products that are sorted into distinct cloud regimes.

  17. Specific ion effects on the self-assembly of ionic surfactants: a molecular thermodynamic theory of micellization with dispersion forces.

    PubMed

    Lukanov, Boris; Firoozabadi, Abbas

    2014-06-10

    The self-assembly of amphiphilic molecules is a key process in numerous biological and chemical systems. When salts are present, the formation and properties of molecular aggregates can be altered dramatically by the specific types of ions in the electrolyte solution. We present a molecular thermodynamic model for the micellization of ionic surfactants that incorporates quantum dispersion forces to account for specific ion effects explicitly through ionic polarizabilities and sizes. We assume that counterions are distributed in the diffuse region according to a modified Poisson-Boltzmann equation and can reach all the way to the micelle surface of charge. Stern layers of steric exclusion or distances of closest approach are not imposed externally; these are accounted for through the counterion radial distribution profiles due to the incorporation of dispersion potentials, resulting in a simple and straightforward treatment. There are no adjustable or fitted parameters in the model, which allows for a priori quantitative prediction of surfactant aggregation behavior based only on the initial composition of the system and the surfactant molecular structure. The theory is validated by accurately predicting the critical micelle concentration (CMC) for the well-studied sodium dodecyl sulfate (SDS) surfactant and its alkaline-counterion derivatives in mono- and divalent salts, as well as the molecular structure parameters of SDS micelles such as aggregation numbers and micelle surface potential.

  18. Effect of backbone chemistry on hybridization thermodynamics of oligonucleic acids: a coarse-grained molecular dynamics simulation study.

    PubMed

    Ghobadi, Ahmadreza F; Jayaraman, Arthi

    2016-02-28

    In this paper we study how varying oligonucleic acid backbone chemistry affects the hybridization/melting thermodynamics of oligonucleic acids. We first describe the coarse-grained (CG) model with tunable parameters that we developed to enable the study of both naturally occurring oligonucleic acids, such as DNA, and their chemically-modified analogues, such as peptide nucleic acids (PNAs) and locked nucleic acids (LNAs). The DNA melting curves obtained using such a CG model and molecular dynamics simulations in an implicit solvent and with explicit ions match with the melting curves obtained using the empirical nearest-neighbor models. We use these CG simulations to then elucidate the effect of backbone flexibility, charge, and nucleobase spacing along the backbone on the melting curves, potential energy and conformational entropy change upon hybridization and base-pair hydrogen bond residence time. We find that increasing backbone flexibility decreases duplex thermal stability and melting temperature mainly due to increased conformational entropy loss upon hybridization. Removing charges from the backbone enhances duplex thermal stability due to the elimination of electrostatic repulsion and as a result a larger energetic gain upon hybridization. Lastly, increasing nucleobase spacing decreases duplex thermal stability due to decreasing stacking interactions that are important for duplex stability.

  19. Effect of Methyl, Hydroxyl, and Chloro Substituents in Position 3 of 3',4',7-Trihydroxyflavylium: Stability, Kinetics, and Thermodynamics.

    PubMed

    Alejo-Armijo, Alfonso; Salido, Sofía; Altarejos, Joaquín; Parola, A Jorge; Gago, Sandra; Basílio, Nuno; Cabrita, Luis; Pina, Fernando

    2016-08-22

    The effect of methyl, hydroxyl, and chloride substituents in position 3 of the 3',4',7-trihydroxyflavylium core structure was studied. The stability, relative energy of each of chemical species (thermodynamics), and their rates of interconversion (kinetics) are very dependent on these substituents. By comparing the mole fraction distribution at equilibrium of the three multistate systems with the parent 3',4',7-trihydroxyflavylium, introduction of a methyl substituent in position 3 increases the mole fraction of hemiketal at the expense of the trans-chalcone and increases the hydration rate very significantly; a hydroxyl substituent in position 3 gives rise to a degradation process, as observed in anthocyanidins. In the case of 3-chloro-3',4',7-trihydroxyflavylium, a dramatic increase of the flavylium cation acidity was observed and a photochromic system can be operated upon irradiation of the respective trans-chalcone in 1 m HCl. According to the photochromic response of 3,3',4',7-tetrahydroxyflavylium and 3',4',7-trihydroxyflavylium, some requirements for a good photochromic performance are discussed.

  20. Nylon 6 electrospun nanofibers mat as effective sorbent for the removal of estrogens: kinetic and thermodynamic studies

    PubMed Central

    2014-01-01

    Nylon 6 electrospun nanofibers mat was prepared via electrospinning for the removal of three estrogens, namely, diethylstilbestrol (DES), dienestrol (DS), and hexestrol (HEX) from aqueous solution. Static adsorption as well as the dynamic adsorption was evaluated by means of batch and dynamic disk flow mode, respectively. The kinetic study indicated that the adsorption of the target compounds could be well fitted by the pseudo-second-order equation, suggesting the intra-particle/membrane diffusion process as the rate-limiting step of the adsorption process. The adsorption equilibrium data were all fitted well to the Freundlich isotherm models, with a maximum adsorption capacity values in the range of 97.71 to 208.95 mg/g, which can be compared to or moderately higher than other sorbents published in the literatures. The dynamic disk mode studies indicated that the mean removal yields of three model estrogens were over 95% with a notable smaller amount of adsorbent (4 mg). Thermodynamic study revealed that the adsorption process was exothermic and spontaneous in nature. Desorption results showed that the adsorption capacity can remain up to 80% after seven times usage. It was suggested that Nylon 6 electrospun nanofibers mat has great potential as a novel effective sorbent material for estrogens removal. PMID:25114645

  1. Separating climate change signals into thermodynamic, lapse-rate and circulation effects: theory and application to the European summer climate

    NASA Astrophysics Data System (ADS)

    Kröner, Nico; Kotlarski, Sven; Fischer, Erich; Lüthi, Daniel; Zubler, Elias; Schär, Christoph

    2016-07-01

    Climate models robustly project a strong overall summer warming across Europe showing a characteristic north-south gradient with enhanced warming and drying in southern Europe. However, the processes that are responsible for this pattern are not fully understood. We here employ an extended surrogate or pseudo-warming approach to disentangle the contribution of different mechanisms to this response pattern. The basic idea of the surrogate technique is to use a regional climate model and apply a large-scale warming to the lateral boundary conditions of a present-day reference simulation, while maintaining the relative humidity (and thus implicitly increasing the specific moisture content). In comparison to previous studies, our approach includes two important extensions: first, different vertical warming profiles are applied in order to separate the effects of a mean warming from lapse-rate effects. Second, a twin-design is used, in which the climate change signals are not only added to present-day conditions, but also subtracted from a scenario experiment. We demonstrate that these extensions provide an elegant way to separate the full climate change signal into contributions from large-scale thermodynamic (TD), lapse-rate (LR), and circulation and other remaining effects (CO). The latter in particular include changes in land-ocean contrast and spatial variations of the SST warming patterns. We find that the TD effect yields a large-scale warming across Europe with no distinct latitudinal gradient. The LR effect, which is quantified for the first time in our study, leads to a stronger warming and some drying in southern Europe. It explains about 50 % of the warming amplification over the Iberian Peninsula, thus demonstrating the important role of lapse-rate changes. The effect is linked to an extending Hadley circulation. The CO effect as inherited from the driving GCM is shown to further amplify the north-south temperature change gradient. In terms of mean summer

  2. Separating climate change signals into thermodynamic, lapse-rate and circulation effects: Theory and application to the European summer climate

    NASA Astrophysics Data System (ADS)

    Kroener, Nico; Kotlarski, Sven; Fischer, Erich; Lüthi, Daniel; Zubler, Elias; Schär, Christoph

    2016-04-01

    Climate models robustly project a strong overall summer warming across Europe showing a characteristic north-south gradient with enhanced warming and drying in southern Europe. However, the processes that are responsible for this pattern are not fully understood. We here employ an extended surrogate or pseudo-warming approach to disentangle the contribution of different mechanisms to this response pattern. The basic idea of the surrogate technique is to use a regional climate model and apply a large-scale warming to the lateral boundary conditions of a present-day reference simulation, while maintaining the relative humidity (and thus implicitly increasing the specific moisture content). In comparison to previous studies, our approach includes two important extensions: First, different vertical warming profiles are applied in order to separate the effects of a mean warming from lapse-rate effects. Second, a twin-design is used, in which the temperature change signal is not only added to present-day conditions, but also subtracted from a scenario experiment. We use the regional climate model COSMO-CLM with a grid spacing of approximately 50 km (EURO-CORDEX EUR-44 setup) using transient simulations (1950-2100) with the RCP8.5 emissions scenario. We demonstrate that the aforementioned extensions provide an elegant way to separate the full climate change signal into contributions from large-scale thermodynamics (LST), lapse-rate (LR) and large-scale circulation (LSC). In our framework the LSC effect also includes effects due to changes in land-sea contrast and the spatial variations of the SST warming pattern. We find that the LST effect yields a large-scale warming across Europe without any distinct latitudinal gradient. The LR effect, which is quantified for the first time in our study, leads to a stronger warming and some drying in Southern Europe. It explains about 50% of the warming amplification over the Iberian Peninsula, thus demonstrating the important role of

  3. The improvement of soil thermodynamics and its effects on land surface meteorology in the IPSL climate model

    NASA Astrophysics Data System (ADS)

    Wang, F.; Cheruy, F.; Dufresne, J.-L.

    2016-01-01

    This paper describes the implementation of an improved soil thermodynamics in the hydrological module of Earth system model (ESM) developed at the Institut Pierre Simon Laplace (IPSL) and its effects on land surface meteorology in the IPSL climate model. A common vertical discretization scheme for the soil moisture and for the soil temperature is adopted. In addition to the heat conduction process, the heat transported by liquid water into the soil is modeled. The thermal conductivity and the heat capacity are parameterized as a function of the soil moisture and the texture. Preliminary tests are performed in an idealized 1-D (one-dimensional) framework and the full model is then evaluated in the coupled land-atmospheric module of the IPSL ESM. A nudging approach is used in order to avoid the time-consuming long-term simulations required to account for the natural variability of the climate. Thanks to this nudging approach, the effects of the modified parameterizations can be modeled. The dependence of the soil thermal properties on moisture and texture lead to the most significant changes in the surface energy budget and in the surface temperature, with the strongest effects on the surface energy budget taking place over dry areas and during the night. This has important consequences on the mean surface temperature over dry areas and during the night and on its short-term variability. The parameterization of the soil thermal properties could therefore explain some of the temperature biases and part of the dispersion over dry areas in simulations of extreme events such as heat waves in state-of-the-art climate models.

  4. The improvement of soil thermodynamics and its effects on land surface meteorology in the IPSL climate model

    NASA Astrophysics Data System (ADS)

    Wang, F.; Cheruy, F.; Dufresne, J.-L.

    2015-10-01

    This paper describes the implementation of an improved soil thermodynamics in the hydrological module of Earth System Model (ESM) developed at the Institut Pierre Simon Laplace (IPSL) and its effects on land surface meteorology in the IPSL climate model. A common vertical discretization scheme for the soil moisture and for the soil temperature is adopted. In addition to the heat conduction process, the heat transported by liquid water into the soil is modeled. The thermal conductivity and the heat capacity are parameterized as a function of the soil moisture and the texture. Preliminary tests are performed in an idealized 1-D framework and the full model is then evaluated in the coupled land/atmospheric module of the IPSL ESM. A nudging approach is used in order to avoid the time-consuming long-term simulations required to account for the natural variability of the climate. Thanks to this nudging approach, the effects of the modified parameterizations can be modeled. The dependence of the soil thermal properties on moisture and texture lead to the most significant changes in the surface energy budget and in the surface temperature, with the strongest effects on the surface energy budget taking place over dry areas and during the night. This has important consequences on the mean surface temperature over dry areas and during the night and on its short-term variability. The parameterization of the soil thermal properties could therefore explain some of the temperature biases and part of the dispersion over dry areas in simulations of extreme events such as heat waves in state-of-the-art climate models.

  5. Impurity doping effects on the orbital thermodynamic properties of hydrogenated graphene, graphane, in Harrison model

    NASA Astrophysics Data System (ADS)

    Yarmohammadi, Mohsen

    2016-12-01

    Using the Harrison model and Green's function technique, impurity doping effects on the orbital density of states (DOS), electronic heat capacity (EHC) and magnetic susceptibility (MS) of a monolayer hydrogenated graphene, chair-like graphane, are investigated. The effect of scattering between electrons and dilute charged impurities is discussed in terms of the self-consistent Born approximation. Our results show that the graphane is a semiconductor and its band gap decreases with impurity. As a remarkable point, comparatively EHC reaches almost linearly to Schottky anomaly and does not change at low temperatures in the presence of impurity. Generally, EHC and MS increases with impurity doping. Surprisingly, impurity doping only affects the salient behavior of py orbital contribution of carbon atoms due to the symmetry breaking.

  6. Effects of Storms on Coastal Vulnerability Through Revisiting Sites Impacted by Super Storm Sandy Offshore Long Island, New York

    NASA Astrophysics Data System (ADS)

    Hosseini, P.; McHugh, C.; Christensen, B. A.; Yong, W. Y.; Delligatti, M.

    2015-12-01

    Recent models indicate that due to climate change storm activity can intensify. Sea level rise as a result of climate change can lead to storm flooding and coastal damage in low-lying populated areas such as NE, USA. The New York metropolitan area experienced one of the highest storm surges in its history during Hurricane Sandy. The peak storm-tide elevation measured by USGS in Jamaica Bay was about 3.5 m, 1.4 m higher than historical measurements in the same area. As part of a National Science Foundation Rapid Response we surveyed from the R/V Pritchard and sampled the bays and inlets along the southern shore of Long Island after Super Storm Sandy in January 2013 and during June 2014 for assessing the impact of the storm. Short-lived radioisotopes, heavy metals and grain size variability were used to track the path of the storm. In 2013 high concentrations of metals (Pb 184 ppm) were deposited on the landward side of barrier islands and were tracked offshore for10 km. In 2014, we revisited the 2013 locations. The offshore, metal enriched mud layer was seen as small inclusions in sand and not present at the surface suggestive that natural processes are cleansing the sea-floor. Inland the cores showed three facies. From the base upwards: 1) coarse sand with low Pb 99 ppm. Interpreted as either sand transported landwards by the storm or in situ; 2) fine-grained, organic rich sediment with the high Pb 443 ppm and interpreted as seaward transport by the storm; 3) organic rich mud with lower Pb 200 ppm was found in the core tops. Most importantly the sea-floor was colonized by tubeworms suggestive that the environment is returning to normal conditions. These results coupled to other regional studies indicate that the storm was catastrophic and resulted in significant sediment transport. The surge brought sand inland modifying channel and inlet depths but most damaging was the seaward surge that brought contaminants offshore. It appears that the bays and inlets are

  7. A Thermodynamic Study of Dopant Interfacial Segregation Effect on Nanostability and Mechanical Properties

    NASA Astrophysics Data System (ADS)

    Wu, Longjia

    Nanoparticles, with great surface area and high surface to volume ratio, have been widely applied in many applications due to their unique size related effects. However, this high surface area character of nanoparticles also brings great excess energy to the whole system, making the system unstable and even causing the failure of nanoparticles, especially at higher temperatures. In order to maintain nanocrystalline structure of the materials, nanostability enhancement is of great significance in nanotechnology. It is well known that the global driving force for particles growth is to eliminate the excess energy brought by surface and grain boundary. Therefore, interfacial energetics has a great influence on the nanostability of the materials. And according to previous studies, dopant interfacial segregation could be a potential way to control the interfacial energetics of the nanoparticles and possibly lead to an improved nanostability. Furthermore, the interfacial energetics even can affect mechanical properties of nano-grain ceramic materials based on recent research. The main goals of the present work were to experimentally measure the interfacial energies of nanoparticles as well as nano-grain ceramics, modify the interfacial energetics through dopant segregation effect and engineer the nanostability and mechanical properties of the nanocrystalline materials through interfacial energetics modification. To achieve this goal, Mn cation has been chosen to introduce Mn interfacial segregation on ceria nanoparticles, and La cation has been added to 12 mol% yttria stabilized zirconia (12YSZ) and magnesium aluminate spinel (MAO) two-phase nano-grain ceramics to cause La interfacial segregation. Both of the dopant segregation phenomena were directly proved by electron energy loss spectroscopy (EELS). To quantify the dopant segregation effect on the interfacial energies, high-temperature oxide melt drop solution calorimetry, water adsorption calorimetry and differential

  8. Thermodynamic effects of laser irradiation of implants placed in bone: an in vitro study.

    PubMed

    Leja, Chris; Geminiani, Alessandro; Caton, Jack; Romanos, Georgios E

    2013-11-01

    Lasers have been proposed for various applications involving dental implants, including uncovering implants and treating peri-implantitis. However, the effect of laser irradiation on the implant surface temperature is only partially known. The aim of this pilot study was to determine the effect of irradiation with diode, carbon dioxide, and Er:YAG lasers on the surface temperature of dental implants placed in bone, in vitro. For this study, one dental implant was placed in a bovine rib. A trephine bur was used to create a circumferential defect to simulate peri-implantitis, and thermocouples were placed at the coronal and apical aspect of the implant. The implant was irradiated for 60 s using four different lasers independently and change in temperature as well as time to reach a 10 °C increase in temperature were recorded. There was wide variability in results among the lasers and settings. Time for a 10 °C increase ranged from 0.9 to over 60 s for the coronal thermocouple and from 18 to over 60 s for the apical thermocouple. Maximum temperature ranged from 5.9 to 70.9 °C coronally and from 1.4 to 23.4 °C apically. During laser irradiation of dental implants, a surface temperature increase beyond the "critical threshold" of 10 °C can be reached after only 18 s.

  9. Effects of Phosphine-Carbene Substitutions on the Electrochemical and Thermodynamic Properties of Nickel Complexes

    SciTech Connect

    Galan, Brandon R.; Wiedner, Eric S.; Helm, Monte L.; Linehan, John C.; Appel, Aaron M.

    2014-05-12

    Nickel(II) complexes containing chelating N-heterocyclic carbene-phosphine ligands ([NiL2](BPh4)2, for which L = [MeIm(CH2)2PR2]) have been synthesized for the purpose of studying how this class of ligand effects the electrochemical properties compared to the nickel bis- diphosphine analogues. The nickel complexes were synthesized and characterized by x-ray crystallography and electrochemical methods. Based on the half wave potentials (E1/2), substitution of an NHC for one of the phosphines in a diphoshine ligand results in shifts in potential to 0.6 V to 1.2 V more negative than the corresponding nickel bis-diphosphine complexes. These quantitative results highlight the substantial effect that NHC ligands can have upon the electronic properties of the metal complexes. BRG, JCL, and AMA acknowledge the support by the US Department of Energy Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. MLH acknoledges the support of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

  10. Thermodynamic study on the effects of β-cyclodextrin inclusion with berberine

    NASA Astrophysics Data System (ADS)

    Yu, Jun-Sheng; Wei, Fang-Di; Gao, Wei; Zhao, Chang-Chun

    2002-01-01

    The fluorescence enhancement of berberine (Berb) as a result of complex with β-cyclodextrin (β-CD) is investigated. The association constants of α-CD and β-CD with Berb are 60 and 137 M -1 at 20 °C in pH 7.20 aqueous solution. Effects of temperature on the forming inclusion complexes of β-CD with Berb have been examined through using fluorescence titration. Enthalpy and entropy values calculated from fluorescence data are -33.7·kJ mol -1 and 74.3 J·mol -1·K -1, respectively. It was found that the dielectric constant of β-CD cavity is about 24 in a rough analogy with absolute alcohol. These results suggest that the extrusion of 'high energy water' molecules from the cavity of β-CD and hydrophobic interaction upon the inclusion complex formation are the main forces of the inclusion reaction. Effect of pH on the association of β-CD with Berb was also studied. Mechanism of the inclusion of β-CD with Berb is further studied by absorption and NMR measurements. Results show that β-CD forms a 1:1 inclusion complex with Berb.

  11. Some thermodynamic considerations on low frequency electromagnetic waves effects on cancer invasion and metastasis

    NASA Astrophysics Data System (ADS)

    Lucia, Umberto; Ponzetto, Antonio

    2017-02-01

    Cell membranes are the reason of the cell energy transfer. In cells energy transfer, thermo-electro-chemical processes and transports phenomena occur through their membranes. Cells can actively modify their behaviours in relation to any change of their environment. They waste heat into their environment. The analysis of irreversibility related to this wasted heat, to the ions transport and the related cell-environment pH changes represents a new useful approach to the study of the cells behaviour. This analysis allows also the explanation of the effects of electromagnetic fields on the cell behaviour, and to suggest how low intensity electromagnetic fields could represent a useful support to the present anticancer therapies.

  12. Effects of electric field on thermodynamics and ordering of a dipolar liquid

    NASA Astrophysics Data System (ADS)

    Johari, G. P.

    2016-10-01

    We propose that an electric field's role in changing the structural disorder may be investigated by comparing the field-induced entropy decrease, ΔES, against the pressure-induced and cooling-induced entropy decreases, ΔpS and ΔTS, respectively, for the same increase in the dielectric α-relaxation time, Δτα, or in the viscosity. If these three quantities are found to be the same, the change in the number of microstates, Δln Ω = ΔS/R, would be the same whether there is an electric field-induced dipole vector alignment, or not. The available data [S. Samanta and R. Richert, J. Chem. Phys. 142, 044504 (2015)] show that ΔES ≅ ΔpS, and ΔES ≅ ΔTS. We further argue that in the case of conformational disorder without hydrodynamics, as for a flexible molecule's orientationally disordered or plastic crystal, ΔTS would be more negative than ΔES for the same increase in Δτα. For cyclo-octanol plastic crystal, whose octyl-ring would lose some of its dielectrically inactive conformational degrees of freedom on cooling, ΔTS is five-times ΔES. Hence the entropy of such crystals may not be related to their τα, an aspect relevant to certain biopolymer crystals. We also mention other effects of E. The findings are relevant to a number of recent studies on the analysis of the effect of electric field on a liquid's properties. The method can be used to study the role of other entropy-altering variables in liquid crystals and ferromagnetic liquids.

  13. Cold modalities with different thermodynamic properties have similar effects on muscular performance and activation.

    PubMed

    Vieira, A; Oliveira, A B; Costa, J R; Herrera, E; Salvini, T F

    2013-10-01

    Although tissue cooling is widely used in the treatment of musculoskeletal injuries there is still controversy about its effects on muscular performance. The combination of cooling and exercise justifies the study of this topic. The aim was to compare the effects of ice pack and cold-water immersion on the muscular performance parameters of plantar flexors and muscular activation of the triceps surae. 41 healthy men (mean age: 22.1 years, SD: 2.9) were randomly assigned to cooling with either ice pack (n=20) or cold-water immersion (n=21). Independent variables were cold modality (ice pack or cold-water immersion) and pre- and post-cooling measurement time. Dependent variables were muscular performance (measured during isometric and concentric contractions of plantar flexors) and electromyography parameters of the triceps surae (median frequency and root mean square amplitude). Dependent-samples t-tests were used to compare pre- and post-cooling data and independent-samples t-tests were used to compare the difference (pre- and post-cooling) between groups. Ice pack increased isometric peak torque (mean: 9.00 Nm, P=0.01) and both cold modalities reduced muscular activation in triceps surae (P<0.0001); Cold-water immersion and ice pack reduced peak torque and total work during dynamic isokinetic contraction at both velocities (mean: -11,00 Nm, P<0.05) and affected muscular activation in different ways. In conclusion, ice pack increases isometric torque, while both ice pack and cold-water immersion decrease concentric muscular performance. These results indicate that these cooling methods should be chosen with caution, considering the type of task required during training or rehabilitation. New studies investigating other muscle groups and joints are necessary.

  14. Microbial diversity arising from thermodynamic constraints

    PubMed Central

    Großkopf, Tobias; Soyer, Orkun S

    2016-01-01

    The microbial world displays an immense taxonomic diversity. This diversity is manifested also in a multitude of metabolic pathways that can utilise different substrates and produce different products. Here, we propose that these observations directly link to thermodynamic constraints that inherently arise from the metabolic basis of microbial growth. We show that thermodynamic constraints can enable coexistence of microbes that utilise the same substrate but produce different end products. We find that this thermodynamics-driven emergence of diversity is most relevant for metabolic conversions with low free energy as seen for example under anaerobic conditions, where population dynamics is governed by thermodynamic effects rather than kinetic factors such as substrate uptake rates. These findings provide a general understanding of the microbial diversity based on the first principles of thermodynamics. As such they provide a thermodynamics-based framework for explaining the observed microbial diversity in different natural and synthetic environments. PMID:27035705

  15. Isothermal titration calorimetry studies of neutral salt effects on the thermodynamics of micelle formation.

    PubMed

    Kresheck, Gordon C

    2009-05-14

    Isothermal titration calorimetry, ITC, was used to determine the enthalpy and heat capacity changes that accompany micelle formation of decyldimethylphosphine oxide, APO10, from 15-79 degrees C in the presence of representative neutral salts from the Hofmeister series. The solutions investigated were water, 0.2, 0.5, and 1.0 NaCl, 0.5 M NaF, KCl, KI, guanidinium chloride (GuHCl) and mannitol, and 0.333 M Na2SO4. The heat capacity change at 25 degrees C (but not the cmc) and the parameter that describes the temperature dependence of the heat capacity change, B (cal/(mol K2)), appear to be correlated. Calculated values of the ion effects on micelle formation from a recent salt ion partitioning model (SPM) of Pegram and Record [J. Phys. Chem. B 2007, 111, 5411-5417] were quantitatively related to the experimental value of the solute free energy increment (SFEI). Use of this model requires a calculation of the solvent accessible area (ASA), which yields values for the extent of hydration of the micelle interior. An alternate method to determine the ASA based on the heat capacity change for micelle formation at 25 degrees C of APO8-12 yielded values for the number of buried carbon atoms (5-12) versus previous estimates (4-8) from analysis of the B parameter.

  16. Effect of silicate structure on thermodynamic properties of calcium silicate melts: Quantitative analysis of Raman spectra

    NASA Astrophysics Data System (ADS)

    Park, Joo Hyun

    2013-05-01

    The distribution of silicate anionic species (Qn units, n=0, 1, 2, 3) and the chemical speciation of oxygen in CaO-SiO2-MO (M=Mn and Mg) slags were investigated by micro-Raman spectroscopic analysis. Furthermore, the thermochemical properties were evaluated using a concentration of free oxygen and a degree of polymerization. A good linear relationship was obtained between sulfide capacity and concentration of free oxygen in the CaO-SiO2 (-MnO) melts at 1500 to 1600 °C. However, even though there was more abundant free oxygen in the CaO-SiO2-MgO system than in the CaO-SiO2 system, the sulfide capacity of the former was lower than the latter, indicating that the sulfur dissolution behavior in the silicate melts cannot be simply explained by the content of free oxygen, because the composition dependency of the stability ratio of oxygen and sulfide ions should be taken into account. The excess free energy of CaO, MgO and MnO linearly decreased as the ln (Q3/Q2) increased. The effect of the degree of polymerization on the excess free energy of mixing of MgO-containing slag was larger than that of MnO-containing slag, which was explained by the difference of the ionization potential between Mn2+ and Mg2+ ions.

  17. Annealing effect on thermodynamic and physical properties of mesoporous silicon: A simulation and nitrogen sorption study

    NASA Astrophysics Data System (ADS)

    Kumar, Pushpendra; Huber, Patrick

    2016-04-01

    Discovery of porous silicon formation in silicon substrate in 1956 while electro-polishing crystalline Si in hydrofluoric acid (HF), has triggered large scale investigations of porous silicon formation and their changes in physical and chemical properties with thermal and chemical treatment. A nitrogen sorption study is used to investigate the effect of thermal annealing on electrochemically etched mesoporous silicon (PS). The PS was thermally annealed from 200˚C to 800˚C for 1 hr in the presence of air. It was shown that the pore diameter and porosity of PS vary with annealing temperature. The experimentally obtained adsorption / desorption isotherms show hysteresis typical for capillary condensation in porous materials. A simulation study based on Saam and Cole model was performed and compared with experimentally observed sorption isotherms to study the physics behind of hysteresis formation. We discuss the shape of the hysteresis loops in the framework of the morphology of the layers. The different behavior of adsorption and desorption of nitrogen in PS with pore diameter was discussed in terms of concave menisci formation inside the pore space, which was shown to related with the induced pressure in varying the pore diameter from 7.2 nm to 3.4 nm.

  18. Valsartan inclusion by methyl-β-cyclodextrin: thermodynamics, molecular modelling, Tween 80 effect and evaluation.

    PubMed

    Chadha, Renu; Bala, Madhu; Arora, Poonam; Jain, D V S; Pissurlenkar, Raghuvir R S; Coutinho, Evans C

    2014-03-15

    The rationale of present study is to investigate the effect of Tween 80 on encapsulation ability of valsartan (VAL) by methyl-β-cyclodextrin (M-β-CD) and to determine the exact mode of binding. Phase solubility studies indicated 1:1 stoichiometry between VAL and M-β-CD both in the presence and absence of Tween 80. The NMR and molecular modelling studies indicated the insertion of both aromatic and aliphatic regions of VAL into the M-β-CD cavity suggesting the coexistence of two 1:1 complexes in equilibrium with each other. The stability constants, K1 (aromatic) and K2 (aliphatic), were enhanced in the presence of Tween 80 as evident by higher value of stability constants (K1 1992.0M(-1), K2 1864.0M(-1)) for ternary system in comparison to binary system (K1 1741.6M(-1), K2 1499.2M(-1)). Efficacy of ternary complex was established by significant decrease in the systolic blood pressure of deoxycorticosterone acetate (DOCA) induced hypertensive rats.

  19. Doping effect on the electronic structure and thermodynamic properties in Ce3Ru4Sn13

    NASA Astrophysics Data System (ADS)

    Kalinowski, L.; Goraus, J.; Witas, P.; Ślebarski, A.

    2016-12-01

    A comprehensive study of heat and electric transport, magnetic, and electronic structure (experiment and calculations) properties is reported for a skutterudite-related Ce3Ru4Sn13 heavy fermion system with the respective substitution of Co and Sb into Ru and Sn sites. Ce3Ru4Sn13 is obtained as a heavy fermion system with high electronic contribution to the specific heat C (T )/T of ˜3 J/K2molCe, and a significant Schottky anomaly below about 10 K. The complex study gives a consistent interpretation of the impact of doping on the crystal electric-field effect and Kondo temperature. For Ce 3Ru4Sn13 we report a field-induced phase transition between the magnetically correlated heavy fermion phase and the single-ion Kondo impurity state, which does not depend on the type of dopant. We also demonstrate that doping does not improve the poor thermoelectric properties of Ce3Ru4Sn13 .

  20. Effect of irreversibility on the thermodynamic characterization of the thermal denaturation of Aspergillus saitoi acid proteinase.

    PubMed Central

    Tello-Solis, S R; Hernandez-Arana, A

    1995-01-01

    The thermal denaturation of the acid proteinase from Aspergillus saitoi was studied by CD and differential scanning calorimetry (DSC). This process seemed to be completely irreversible, as protein samples that were heated to temperatures at which the transition had been completed and then cooled at 25 degrees C did not show any reversal of the change in the CD signal. Similar results were obtained with DSC. Nevertheless, we were able to detect the presence of reversibly unfolded species in experiments in which the enzyme solution was heated to a temperature within the transition region, followed by rapid cooling at 25 degrees C. Accordingly, the denaturation of behaviour of the acid proteinase seems to be consistent with the existence of one (or more) reversible unfolding transition followed by an irreversible step. The van't Hoff enthalpy, delta HvH, which corresponds to the reversible transition was calculated from extrapolation to infinite heating rate as 310 kJ.mol-1. This parameter was also determined from direct estimation of the equilibrium constant at several temperatures (delta HvH = 176 kJ.mol-1). Comparison of the average delta HvH with the calorimetric enthalpy (delta Hcal. = 770 kJ.mol-1) gave a value of 3.2 for the delta Hcal./delta HvH ratio, indicating that the molecular structure of the enzyme is probably formed by three or four cooperative regions, a number similar to that of the acid proteinase, pepsin. It should be noted that a completely different conclusion would be obtained from a straightforward analysis of the calorimetric curves, disregarding the effect of irreversibility on the denaturation process. PMID:7487958

  1. Thermodynamic characterization of the biocompatible ionic liquid effects on protein model compounds and their functional groups.

    PubMed

    Attri, Pankaj; Venkatesu, Pannuru

    2011-04-14

    The stability of proteins under co-solvent conditions is dependant on the nature of the co-solvent; the co-solvent can alter a protein's properties and structural effects through bimolecular interactions between its functional groups and co-solvent particles. Ionic liquids (ILs) represent a rather diverse class of co-solvents that are combinations of different ions, which are liquids at or close to room temperature. To quantify the bimolecular interactions of protein functional groups with biocompatible ILs, we report the systematic and quantitative apparent transfer free energies (ΔG'(tr)) of a homologous series of cyclic dipeptides (CDs) from water to aqueous solutions of ILs through solubility measurements, as a function of IL concentration at 25 °C under atmospheric pressure. The materials investigated in the present work included the CDs of cyclo(Gly-Gly), cyclo(Ala-Gly), cyclo(Ala-Ala), cyclo(Leu-Ala), and cyclo(Val-Val). The ILs used such as diethylammonium acetate ([Et(2)NH][CH(3)COO], DEAA), triethylammonium acetate ([Et(3)NH][CH(3)COO], TEAA), diethylammonium dihydogen phosphate ([Et(3)NH][H(2)PO(4)], DEAP), triethylammonium dihydogen phosphate ([Et(3)NH][H(2)PO(4)], TEAP), diethylammonium sulfate ([Et(3)NH][HSO(4)], DEAS) and triethylammonium sulfate ([Et(3)NH][HSO(4)], TEAS). We observed positive values of ΔG'(tr) for CDs from water to ILs, indicating that interactions between ILs and CDs are unfavourable, which leads to stabilization of the native structure of CDs. The experimental results were further used for estimating the transfer free energies (Δg'(tr)) of the peptide bond (-CONH-), the peptide backbone unit (-CH(2)C=ONH-), and various functional groups from water to IL solutions. Our results explicitly elucidate that a series of all ammonium ILs act as stabilizers for tested model compounds through the exclusion of ILs from CDs surface.

  2. The effect of pyridyl substituents on the thermodynamics of porphyrin binding to G-quadruplex DNA.

    PubMed

    Rowland, Gerald B; Barnett, Kerry; Dupont, Jesse I; Akurathi, Gopalakrishna; Le, Vu H; Lewis, Edwin A

    2013-12-01

    Most of the G-quadruplex interactive molecules reported to date contain extended aromatic flat ring systems and are believed to bind principally by π-π stacking on the end G-tetrads of the quadruplex structure. One such molecule, TMPyP4, (5,10,15,20-tetra(N-methyl-4-pyridyl)porphyrin), exhibits high affinity and some selectivity for G-quadruplex DNA over duplex DNA. Although not a realistic drug candidate, TMPyP4 is used in many nucleic acid research laboratories as a model ligand for the study of small molecule G-quadruplex interactions. Here we report on the synthesis and G-quadruplex interactions of four new cationic porphyrin ligands having only 1, 2, or 3 (N-methyl-4-pyridyl) substituents. The four new ligands are: P(5) (5-(N-methyl-4-pyridyl)porphyrin), P(5,10) (5,10-di(N-methyl-4-pyridyl)porphyrin), P(5,15) (5,15-di(N-methyl-4-pyridyl)porphyrin), and P(5,10,15) (5,10,15-tri(N-methyl-4-pyridyl)porphyrin). Even though these compounds have been previously synthesized, we report alternative synthetic routes that are more efficient and that result in higher yields. We have used ITC, CD, and ESI-MS to explore the effects of the number of N-methyl-4-pyridyl substituents and the substituent position on the porphyrin on the G-quadruplex binding energetics. The relative affinities for binding these ligands to the WT Bcl-2 promoter sequence G-quadruplex are: K(TMPyP4)≈K(P)(5,15)>KP(5,10,15)>KP(5,10), KP(5). The saturation stoichiometry is 2:1 for both P(5,15) and P(5,10,15), while neither P(5) nor P(5,10) exhibit significant complex formation with the WT Bcl-2 promoter sequence G-quadruplex. Additionally, binding of P(5,15) appears to interact by an 'intercalation mode' while P(5,10,15) appears to interact by an 'end-stacking mode'.

  3. Radiolytic Cryovolcanism Revisited

    NASA Astrophysics Data System (ADS)

    Cooper, J. F.; Cooper, P. D.; Sittler, E. C.; Wesenberg, R. P.

    2013-12-01

    Active geysers of water vapor and ice grains from the south pole of Enceladus are not yet definitively explained in terms of energy sources and processes. Other instances of hot (Io) and cold (Mars, Triton) volcanism beyond Earth are known if not fully understood. We revisit, in comparison to other models, the 'Old Faithful' theory of radiolytic gas-driven cryovolcanism first proposed by Cooper et al. [Plan. Sp. Sci. 2009]. In the energetic electron irradiation environment of Enceladus within Saturn's magnetosphere, a 10-percent duty cycle could be maintained for current geyser activity driven by gases from oxidation of ammonia to N2 and methane to CO2 in the thermal margins of a south polar sea. Much shorter duty cycles down to 0.01 percent would be required to account for thermal power output up to 16 GW, Steady accumulation of oxidant energy over four billion years could have powered all Enceladus emissions over the past four hundred thousand to four hundred million years. There could be separate energy sources driving mass flow and thermal emission over vastly different time scales. Since episodic tidal dissipation on 10 Myr time scales at 0.1 - 1 Gyr intervals [O'Neill and Nimmo, Nature 2010], and thus duty cycles 1 - 10 percent, could heat the polar sea to the current level, the radiolytic energy source could easily power and modulate the geyser mass flow on million-year time scales. Maximum thermal emission temperature 223 K [Abramov and Spencer, Icarus 2009] hints at thermal buffering in the basal and vent wall layers by a 1:1 H2O:H2O2 radiolytic eutectic, assuming deep ice crust saturation with H2O2 from long cumulative surface irradiation and downward ice convection. Due to density stratification the peroxide eutectic and salt water layers could separate, so that the denser peroxide layer (1.2 g/cc) descends to the polar sea while the lighter salt water (1.05 g/cc) rises along separate channels. Methane reservoirs could be found dissolved into the polar

  4. A thermodynamic tank model for studying the effect of higher hydrocarbons on natural gas storage in metal-organic frameworks

    SciTech Connect

    Zhang, HD; Deria, P; Farha, OK; Hupp, JT; Snurr, RQ

    2015-01-01

    Metal-organic frameworks (MOFs) are promising materials for storing natural gas in vehicular applications. Evaluation of these materials has focused on adsorption of pure methane, although commercial natural gas also contains small amounts of higher hydrocarbons such as ethane and propane, which adsorb more strongly than methane. There is, thus, a possibility that these higher hydrocarbons will accumulate in the MOF after multiple operating (adsorption/desorption) cycles, and reduce the storage capacity. To study the net effect of ethane and propane on the performance of an adsorbed natural gas (ANG) tank, we developed a mathematical model based on thermodynamics and mass balance equations that describes the state of the tank at any instant. The required inputs are the pure-component isotherms, and mixture adsorption data are calculated using the Ideal Adsorbed Solution Theory (IAST). We focused on how the "deliverable energy'' provided by the ANG tank to the engine changed over 200 operating cycles for a sample of 120 MOF structures. We found that, with any MOF, the ANG tank performance monotonically declines during early operating cycles until a "cyclic steady state'' is reached. We determined that the best materials when the fuel is 100% methane are not necessarily the best when the fuel includes ethane and propane. Among the materials tested, some top MOFs are MOF-143 > NU-800 > IRMOF-14 > IRMOF-20 > MIL-100 > NU-125 > IRMOF-1 > NU-111. MOF-143 is predicted to deliver 5.43 MJ L-1 of tank to the engine once the cyclic steady state is reached. The model also provided insights that can assist in future work to discover more promising adsorbent materials for natural gas storage.

  5. Solvent effect on molecular structure, IR spectra, thermodynamic properties and chemical stability of zoledronic acid: DFT study.

    PubMed

    Liu, Qingzhu; Qiu, Ling; Wang, Yang; Lv, Gaochao; Liu, Guiqing; Wang, Shanshan; Lin, Jianguo

    2016-04-01

    Zoledronic acid (ZL) has been used widely for treating skeletal diseases because of its high potency in inhibiting bone resorption. A detailed understanding of its physicochemical characteristics may be of great significance in both medicinal chemistry and structural biology for the design of novel bisphosphonates with higher activity. In the present work, the monoclinic (IM) and triclinic (IT) polymorphs of ZL in the gas phase and the aqueous phase were studied by density functional theory (DFT) method at the B3LYP/6-311++G** level. The polarizable continuum model (PCM) was employed to study the solvent effect on structures and properties. The optimized IM and IT conformations in both phases are in reasonable agreement with the experimental structures with the overall mean absolute percent deviation (MAPD%) less than 3.1 %. The presence of intramolecular hydrogen bond within both conformations was identified in the solvent. The IR spectra were simulated and assigned in detail, which agreed well with the experimental data. The intramolecular hydrogen bonding interactions resulted in the shift of vibrational frequencies of hydroxyl to the low band by 12-22 cm(-1) and 24-26 cm(-1) for IM and IT conformations, respectively. Their thermodynamic properties were also calculated based on the harmonic vibrational analysis, including standard heat capacity (C(°)p,m), entropy (S(°)m), and enthalpy (H(°)m). The molecular stability, hydrogen bonding interaction and other electronic properties have been further analyzed by the natural bond orbital (NBO), atoms in molecules (AIM), molecular electrostatic potential (MEP) and frontier molecular orbital (FMO) analysis.

  6. Influence of velocity effects on the shape of N2 (and air) broadened H2O lines revisited with classical molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Ngo, N. H.; Tran, H.; Gamache, R. R.; Bermejo, D.; Domenech, J.-L.

    2012-08-01

    The modeling of the shape of H2O lines perturbed by N2 (and air) using the Keilson-Storer (KS) kernel for collision-induced velocity changes is revisited with classical molecular dynamics simulations (CMDS). The latter have been performed for a large number of molecules starting from intermolecular-potential surfaces. Contrary to the assumption made in a previous study [H. Tran, D. Bermejo, J.-L. Domenech, P. Joubert, R. R. Gamache, and J.-M. Hartmann, J. Quant. Spectrosc. Radiat. Transf. 108, 126 (2007)], 10.1016/j.jqsrt.2007.03.009, the results of these CMDS show that the velocity-orientation and -modulus changes statistically occur at the same time scale. This validates the use of a single memory parameter in the Keilson-Storer kernel to describe both the velocity-orientation and -modulus changes. The CMDS results also show that velocity- and rotational state-changing collisions are statistically partially correlated. A partially correlated speed-dependent Keilson-Storer model has thus been used to describe the line-shape. For this, the velocity changes KS kernel parameters have been directly determined from CMDS, while the speed-dependent broadening and shifting coefficients have been calculated with a semi-classical approach. Comparisons between calculated spectra and measurements of several lines of H2O broadened by N2 (and air) in the ν3 and 2ν1 + ν2 + ν3 bands for a wide range of pressure show very satisfactory agreement. The evolution of non-Voigt effects from Doppler to collisional regimes is also presented and discussed.

  7. Influence of velocity effects on the shape of N2 (and air) broadened H2O lines revisited with classical molecular dynamics simulations.

    PubMed

    Ngo, N H; Tran, H; Gamache, R R; Bermejo, D; Domenech, J-L

    2012-08-14

    The modeling of the shape of H(2)O lines perturbed by N(2) (and air) using the Keilson-Storer (KS) kernel for collision-induced velocity changes is revisited with classical molecular dynamics simulations (CMDS). The latter have been performed for a large number of molecules starting from intermolecular-potential surfaces. Contrary to the assumption made in a previous study [H. Tran, D. Bermejo, J.-L. Domenech, P. Joubert, R. R. Gamache, and J.-M. Hartmann, J. Quant. Spectrosc. Radiat. Transf. 108, 126 (2007)], the results of these CMDS show that the velocity-orientation and -modulus changes statistically occur at the same time scale. This validates the use of a single memory parameter in the Keilson-Storer kernel to describe both the velocity-orientation and -modulus changes. The CMDS results also show that velocity- and rotational state-changing collisions are statistically partially correlated. A partially correlated speed-dependent Keilson-Storer model has thus been used to describe the line-shape. For this, the velocity changes KS kernel parameters have been directly determined from CMDS, while the speed-dependent broadening and shifting coefficients have been calculated with a semi-classical approach. Comparisons between calculated spectra and measurements of several lines of H(2)O broadened by N(2) (and air) in the ν(3) and 2ν(1) + ν(2) + ν(3) bands for a wide range of pressure show very satisfactory agreement. The evolution of non-Voigt effects from Doppler to collisional regimes is also presented and discussed.

  8. Effect of the specific surface area on thermodynamic and kinetic properties of nanoparticle anatase TiO2 in lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Madej, Edyta; Klink, Stefan; Schuhmann, Wolfgang; Ventosa, Edgar; La Mantia, Fabio

    2015-11-01

    Anatase TiO2 nanoparticles with a specific surface area of 100 m2 g-1 and 300 m2 g-1 have been investigated as negative insertion electrode material for lithium-ion batteries. Galvanostatic intermittent titration (GITT) and electrochemical impedance spectroscopy (EIS) were used to investigate the effect of the specific surface area on the performance of the material. GITT was performed at C/10 rate, followed by an EIS measurement after each relaxation step. Separation of kinetic and thermodynamic contributions to the overpotential of the phase transformation on Li+ (de-)insertion allowed revealing a dependency of both terms on the specific surface area. The material with higher surface area undergoes intrinsic transformation during the initial cycles affecting the thermodynamics of (de-)insertion while the sample with lower surface area shows large and asymmetric kinetic hindrances. For the material with 15 nm particles, Li+ de-insertion appears to have a higher resistance than lithium insertion.

  9. Study of the thermodynamic properties of CeO{sub 2} from ab initio calculations: The effect of phonon-phonon interaction

    SciTech Connect

    Niu, Zhen-Wei; Zeng, Zhao-Yi; Hu, Cui-E; Cai, Ling-Cang; Chen, Xiang-Rong

    2015-01-07

    The thermodynamic properties of CeO{sub 2} have been reevaluated by a simple but accurate scheme. All our calculations are based on the self-consistent ab initio lattice dynamical (SCAILD) method that goes beyond the quasiharmonic approximation. Through this method, the effects of phonon-phonon interactions are included. The obtained thermodynamic properties and phonon dispersion relations are in good agreement with experimental data when considering the correction of phonon-phonon interaction. We find that the correction of phonon-phonon interaction is equally important and should not be neglected. At last, by comparing with quasiharmonic approximation, the present scheme based on SCAILD method is probably more suitable for high temperature systems.

  10. Thermodynamics of phase coexistence and metal-nonmetal transition in mercury: assessment of effective potentials via expanded Wang-Landau simulations.

    PubMed

    Desgranges, Caroline; Delhommelle, Jerome

    2014-03-20

    We present molecular simulation results on the thermodynamics of phase transitions (specifically, the vapor-liquid and metal-nonmetal transitions) in mercury, as predicted by effective potential models. We use a recently developed method, known as Expanded Wang-Landau simulations, to determine the grand-canonical partition function of systems of mercury atoms. Using the statistical mechanics formalism, we are then able to determine all thermodynamic properties of the system, including the Gibbs free energy and entropy. Prior experimental and theoretical work has emphasized the strong interplay between the vapor-liquid coexistence and the metal-nonmetal transition. We therefore start by assessing the accuracy of the effective potentials considered in this work through a comparison to the available experimental data. We then analyze the thermodynamics of the nonmetal liquid-metal liquid transition, characterized by sharp variations in the rate of change of Gibbs free energy and enthalpy as a function of density. We also identify a crossover density (10.5 g/cm(3)) consistent with the results of recent ab initio calculations and with the experiment.

  11. Coherence and measurement in quantum thermodynamics

    PubMed Central

    Kammerlander, P.; Anders, J.

    2016-01-01

    Thermodynamics is a highly successful macroscopic theory widely used across the natural sciences and for the construction of everyday devices, from car engines to solar cells. With thermodynamics predating quantum theory, research now aims to uncover the thermodynamic laws that govern finite size systems which may in addition host quantum effects. Recent theoretical breakthroughs include the characterisation of the efficiency of quantum thermal engines, the extension of classical non-equilibrium fluctuation theorems to the quantum regime and a new thermodynamic resource theory has led to the discovery of a set of second laws for finite size systems. These results have substantially advanced our understanding of nanoscale thermodynamics, however putting a finger on what is genuinely quantum in quantum thermodynamics has remained a challenge. Here we identify information processing tasks, the so-called projections, that can only be formulated within the framework of quantum mechanics. We show that the physical realisation of such projections can come with a non-trivial thermodynamic work only for quantum states with coherences. This contrasts with information erasure, first investigated by Landauer, for which a thermodynamic work cost applies for classical and quantum erasure alike. Repercussions on quantum work fluctuation relations and thermodynamic single-shot approaches are also discussed. PMID:26916503

  12. Coherence and measurement in quantum thermodynamics.

    PubMed

    Kammerlander, P; Anders, J

    2016-02-26

    Thermodynamics is a highly successful macroscopic theory widely used across the natural sciences and for the construction of everyday devices, from car engines to solar cells. With thermodynamics predating quantum theory, research now aims to uncover the thermodynamic laws that govern finite size systems which may in addition host quantum effects. Recent theoretical breakthroughs include the characterisation of the efficiency of quantum thermal engines, the extension of classical non-equilibrium fluctuation theorems to the quantum regime and a new thermodynamic resource theory has led to the discovery of a set of second laws for finite size systems. These results have substantially advanced our understanding of nanoscale thermodynamics, however putting a finger on what is genuinely quantum in quantum thermodynamics has remained a challenge. Here we identify information processing tasks, the so-called projections, that can only be formulated within the framework of quantum mechanics. We show that the physical realisation of such projections can come with a non-trivial thermodynamic work only for quantum states with coherences. This contrasts with information erasure, first investigated by Landauer, for which a thermodynamic work cost applies for classical and quantum erasure alike. Repercussions on quantum work fluctuation relations and thermodynamic single-shot approaches are also discussed.

  13. Coherence and measurement in quantum thermodynamics

    NASA Astrophysics Data System (ADS)

    Kammerlander, P.; Anders, J.

    2016-02-01

    Thermodynamics is a highly successful macroscopic theory widely used across the natural sciences and for the construction of everyday devices, from car engines to solar cells. With thermodynamics predating quantum theory, research now aims to uncover the thermodynamic laws that govern finite size systems which may in addition host quantum effects. Recent theoretical breakthroughs include the characterisation of the efficiency of quantum thermal engines, the extension of classical non-equilibrium fluctuation theorems to the quantum regime and a new thermodynamic resource theory has led to the discovery of a set of second laws for finite size systems. These results have substantially advanced our understanding of nanoscale thermodynamics, however putting a finger on what is genuinely quantum in quantum thermodynamics has remained a challenge. Here we identify information processing tasks, the so-called projections, that can only be formulated within the framework of quantum mechanics. We show that the physical realisation of such projections can come with a non-trivial thermodynamic work only for quantum states with coherences. This contrasts with information erasure, first investigated by Landauer, for which a thermodynamic work cost applies for classical and quantum erasure alike. Repercussions on quantum work fluctuation relations and thermodynamic single-shot approaches are also discussed.

  14. Escitalopram dose-response revisited: an alternative psychometric approach to evaluate clinical effects of escitalopram compared to citalopram and placebo in patients with major depression.

    PubMed

    Bech, Per; Tanghøj, Per; Cialdella, Philippe; Andersen, Henning Friis; Pedersen, Anders Gersel

    2004-09-01

    In continuation of a previous psychometric analysis of dose-response data for citalopram in depression, the corresponding study data for escitalopram is of interest, since escitalopram is the active enantiomer of citalopram and because citalopram was used as the active control. Revisiting those corresponding data, the psychometric properties of the Montgomery-Asberg Depression Scale (MADRS) and the Hamilton Depression Scale (HAMD) were investigated by focusing on the unidimensional HAMD6 and MADRS6. Effect sizes were calculated and compared for two dosages of escitalopram (10 mg and 20 mg daily) and between each of these two dosages and 40 mg citalopram daily. The results showed that the three depression scales MADRS6, MADRS10 and HAMD6 were psychometrically acceptable (coefficient of homogeneity of 0.40 or higher). In the severely depressed patients (MADRS10> or =30) a rather clear dose-response relationship for escitalopram was seen on all three scales after 6 and 8 wk of therapy. Thus, the effect size for 10 mg escitalopram ranged from 0.28 to 0.38 while the effect sizes for 20 mg escitalopram ranged from 0.57 to 0.77. This difference was statistically significant (p<0.01). The effect size for 40 mg citalopram ranged from 0.36 to 0.47, which is within the range found for 40 mg citalopram in our previous dose-response analysis of citalopram after 6 wk of therapy. The numerically largest difference between 20 mg escitalopram and 40 mg citalopram was seen after 8 wk of therapy for MADRS10 (effect size 0.71 vs. 0.37). An item analysis identified 'suicidal thoughts' to be the most discriminating item in this respect. These results for the severely depressed patients were confirmed by the patients self-reported quality of life evaluation. When all included patients were analysed, however, no clear dose-response relationship was seen. In conclusion, a dose-response relationship for escitalopram was seen in the severely depressed patients on all outcome scales after 6

  15. Effect of deviation from local thermodynamic equilibrium on the Goldberg-Unno method. [turbulence effects on optical density in the solar photosphere

    NASA Technical Reports Server (NTRS)

    Troyan, V. I.

    1974-01-01

    The dependence of turbulent velocity on optical depth was studied by use of the Goldberg-Unno method, with allowance made for the influence of deviation from the local thermodynamic equilibrium. It was found that allowance for deviation from local thermodynamic equilibrium displaces the curve of dependence of turbulent velocity on optical depth along two axes.

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

    ERIC Educational Resources Information Center

    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…

  17. Girl Number 20 Revisited: Feminist Literacies in New Hard Times

    ERIC Educational Resources Information Center

    Gonick, Marnina

    2007-01-01

    This paper revisits the question of "voice" in the context of neo-liberal social and educational reform. "Voice" has been one of the key concepts of feminist and critical pedagogies in the theory and practice of producing social transformation. I argue in this paper, that the political effectiveness of this concept needs to be…

  18. pH and solvent H/D isotope effects on the thermodynamics and kinetics of electron transfer for electrode-immobilized native and urea-unfolded stellacyanin.

    PubMed

    Ranieri, Antonio; Battistuzzi, Gianantonio; Borsari, Marco; Bortolotti, Carlo Augusto; Di Rocco, Giulia; Sola, Marco

    2012-10-23

    The thermodynamics of Cu(II) to Cu(I) reduction and the kinetics of the electron transfer (ET) process for Rhus vernicifera stellacyanin (STC) immobilized on a decane-1-thiol coated gold electrode have been measured through cyclic voltammetry at varying pH and temperature, in the presence of urea and in D(2)O. Immobilized STC undergoes a limited conformational change that mainly results in an enhanced exposure of one or both copper binding histidines to solvent which slightly stabilizes the cupric state and increases histidine basicity. The large immobilization-induced increase in the pK(a) for the acid transition (from 4.5 to 6.3) makes this electrode-SAM-protein construct an attractive candidate as a biomolecular ET switch operating near neutral pH in molecular electronics. Such a potential interest is increased by the robustness of this interface against chemical unfolding as it undergoes only moderate changes in the reduction thermodynamics and in the ET rate in the presence of up to 8 M urea. The sensitivity of these parameters to solvent H/D isotope effects testifies to the role of protein solvation as effector of the thermodynamics and kinetics of ET.

  19. Stirling Engine Gets Revisited

    ERIC Educational Resources Information Center

    Thompson, Frank

    2010-01-01

    One of the basic truths regarding energy conversion is that no thermodynamic cycle can be devised that is more efficient than a Carnot cycle operating between the same temperature limits. The efficiency of the Stirling cycle (patented by Rev. Robert Stirling in 1816) can approach that of the Carnot cycle and yet has not had the commercial success…

  20. The effect of thermodynamic properties of solvent mixtures explains the difference between methanol and ethanol in C.antarctica lipase B catalyzed alcoholysis.

    PubMed

    Sasso, Francesco; Kulschewski, Tobias; Secundo, Francesco; Lotti, Marina; Pleiss, Jürgen

    2015-11-20

    Kinetic modelling, molecular modelling, and experimental determination of the initial reaction velocity of lipase-catalyzed alcoholysis were combined to study the effect of the alcohol substrate to catalytic activity. The model system consisted of methanol or ethanol at varying concentrations, vinyl acetate as ester substrate 15.2% (v/v), toluene as organic solvent, water at a controlled thermodynamic activity of 0.09, and C. antarctica lipase B as enzyme. For both alcohol substrates, the initial reaction velocity increased sharply at low concentrations and reached a maximum at 0.7% (v/v) for methanol and 2% (v/v) for ethanol. For higher concentrations, the reaction rate decreased to a level of 74% and 60% of the peak value, respectively, due to substrate inhibition. The concentration dependency was described by a kinetic model, including a ping-pong bi-bi mechanism and competitive inhibition by the alcohol, and confirmed previous observations that methanol is more efficiently inhibiting the enzyme than ethanol. However, if the initial reaction velocity was expressed in terms of thermodynamic activity of the two alcohol substrates, the maximum of initial reaction velocity was similar for methanol (a MeOH(max)=0.19) and ethanol (a EtOH(max)=0.21). This was confirmed by molecular modelling which resulted in similar KM (0.22 and 0.19) and Ki values (0.44 and 0.49) for methanol and ethanol, respectively, if expressed in thermodynamic activities. Thus, the experimentally observed difference between methanol and ethanol is not due to differences in interaction with the enzyme but is a consequence of the thermodynamics of the substrate-solvent mixture. For low concentrations in toluene, the activity coefficient of methanol is 40% higher than the activity coefficient of ethanol (γ MeOH=8.5, γ EtOH=6.1).

  1. Quantum duel revisited

    NASA Astrophysics Data System (ADS)

    Schmidt, Alexandre G. M.; Paiva, Milena M.

    2012-03-01

    We revisit the quantum two-person duel. In this problem, both Alice and Bob each possess a spin-1/2 particle which models dead and alive states for each player. We review the Abbott and Flitney result—now considering non-zero α1 and α2 in order to decide if it is better for Alice to shoot or not the second time—and we also consider a duel where players do not necessarily start alive. This simple assumption allows us to explore several interesting special cases, namely how a dead player can win the duel shooting just once, or how can Bob revive Alice after one shot, and the better strategy for Alice—being either alive or in a superposition of alive and dead states—fighting a dead opponent.

  2. ``Robinson's sum rule'' revisited

    NASA Astrophysics Data System (ADS)

    Orlov, Yuri F.

    2010-02-01

    This discussion revisits two articles on synchrotron radiation damping published in 1958, one by this author and Evgeny K. Tarasov [Zh. Eksp. Teor. Fiz. 34, 651 (1958)ZETFA70044-4510; Sov. Phys. JETP 34, 449 (1958)SPHJAR0038-5646], and one by Kenneth W. Robinson [Phys. Rev. 111, 373 (1958)PHRVAO0031-899X10.1103/PhysRev.111.373]. The latter is the source of what is known as “Robinson’s sum rule.” Both present the familiar rule, but with very different proofs and calculations of concrete damping decrements. Comparative analysis of these differences reveals serious flaws in Robinson’s proof and calculations.

  3. Polite Theories Revisited

    NASA Astrophysics Data System (ADS)

    Jovanović, Dejan; Barrett, Clark

    The classic method of Nelson and Oppen for combining decision procedures requires the theories to be stably-infinite. Unfortunately, some important theories do not fall into this category (e.g. the theory of bit-vectors). To remedy this problem, previous work introduced the notion of polite theories. Polite theories can be combined with any other theory using an extension of the Nelson-Oppen approach. In this paper we revisit the notion of polite theories, fixing a subtle flaw in the original definition. We give a new combination theorem which specifies the degree to which politeness is preserved when combining polite theories. We also give conditions under which politeness is preserved when instantiating theories by identifying two sorts. These results lead to a more general variant of the theorem for combining multiple polite theories.

  4. Thermodynamics of Error Correction

    NASA Astrophysics Data System (ADS)

    Sartori, Pablo; Pigolotti, Simone

    2015-10-01

    Information processing at the molecular scale is limited by thermal fluctuations. This can cause undesired consequences in copying information since thermal noise can lead to errors that can compromise the functionality of the copy. For example, a high error rate during DNA duplication can lead to cell death. Given the importance of accurate copying at the molecular scale, it is fundamental to understand its thermodynamic features. In this paper, we derive a universal expression for the copy error as a function of entropy production and work dissipated by the system during wrong incorporations. Its derivation is based on the second law of thermodynamics; hence, its validity is independent of the details of the molecular machinery, be it any polymerase or artificial copying device. Using this expression, we find that information can be copied in three different regimes. In two of them, work is dissipated to either increase or decrease the error. In the third regime, the protocol extracts work while correcting errors, reminiscent of a Maxwell demon. As a case study, we apply our framework to study a copy protocol assisted by kinetic proofreading, and show that it can operate in any of these three regimes. We finally show that, for any effective proofreading scheme, error reduction is limited by the chemical driving of the proofreading reaction.

  5. Circular revisit orbits design for responsive mission over a single target

    NASA Astrophysics Data System (ADS)

    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.

  6. Solvent effect on the complex formation of a crown ether derivative with sodium and potassium ions. Thermodynamic background of selectivity

    NASA Astrophysics Data System (ADS)

    Li, Yin; Huszthy, Péter; Móczár, Ildikó; Szemenyei, Balázs; Kunsági-Máté, Sándor

    2013-01-01

    The complexation properties of dimethyl-pyridino-18-crown-6 ether (M2P18C6) with Na+ and K+ in different primary alcohols including methanol (MeOH), ethanol (EtOH) and n-propanol (n-PrOH) were investigated by UV-vis spectroscopy. Stability constants and thermodynamic parameters have been determined applying the van't Hoff theory. In the cases of both Na+ and K+ the stability constants increase with decreasing permittivity of the solvent used. M2P18C6 always exhibits better affinity to K+ in each alcoholic solution compared to Na+. Thermodynamic studies suggest that in both cases there is a correlation between the permittivity of the solvent and the enthalpy and entropy change of complex formation.

  7. Pressure effect on structural, elastic, and thermodynamic properties of tetragonal B{sub 4}C{sub 4}

    SciTech Connect

    Zheng, Baobing; Zhang, Meiguang; Luo, Hong-Gang

    2015-03-15

    The compressibility, elastic anisotropy, and thermodynamic properties of the recently proposed tetragonal B{sub 4}C{sub 4} (t-B{sub 4}C{sub 4}) are investigated under high temperature and high pressure by using of first-principles calculations method. The elastic constants, bulk modulus, shear modulus, Young’s modulus, Vickers hardness, Pugh’s modulus ratio, and Poisson’s ratio for t-B{sub 4}C{sub 4} under various pressures are systematically explored, the obtained results indicate that t-B{sub 4}C{sub 4} is a stiffer material. The elastic anisotropies of t-B{sub 4}C{sub 4} are discussed in detail under pressure from 0 GPa to 100 GPa. The thermodynamic properties of t-B{sub 4}C{sub 4}, such as Debye temperature, heat capacity, and thermal expansion coefficient are investigated by the quasi-harmonic Debye model.

  8. Effects of dynamic heterogeneity and density scaling of molecular dynamics on the relationship among thermodynamic coefficients at the glass transition

    SciTech Connect

    Koperwas, K. Grzybowski, A.; Grzybowska, K.; Wojnarowska, Z.; Paluch, M.

    2015-07-14

    In this paper, we define and experimentally verify thermodynamic characteristics of the liquid-glass transition, taking into account a kinetic origin of the process. Using the density scaling law and the four-point measure of the dynamic heterogeneity of molecular dynamics of glass forming liquids, we investigate contributions of enthalpy, temperature, and density fluctuations to spatially heterogeneous molecular dynamics at the liquid-glass transition, finding an equation for the pressure coefficient of the glass transition temperature, dTg/dp. This equation combined with our previous formula for dTg/dp, derived solely from the density scaling criterion, implies a relationship among thermodynamic coefficients at Tg. Since this relationship and both the equations for dTg/dp are very well validated using experimental data at Tg, they are promising alternatives to the classical Prigogine-Defay ratio and both the Ehrenfest equations in case of the liquid-glass transition.

  9. Thermodynamic simulation of the effect of slag chemistry on the corrosion behavior of alumina-chromia refractory

    NASA Astrophysics Data System (ADS)

    Zhao, Shi-xian; Cai, Bin-li; Sun, Hong-gang; Wang, Gang; Li, Hong-xia; Song, Xiao-yan

    2016-12-01

    The corrosion behavior of alumina-chromia refractory against two kinds of industrial slags (coal slag and iron smelting slag) at 1550°C was investigated via thermodynamic simulations. In the proposed simulation model, the initial slag first attacks the matrix and surface aggregates and subsequently attacks the inner aggregates. The simulation results indicate that the slag chemistry strongly affects the phase formation and corrosion behavior of the refractory brick. Greater amounts of alumina were dissolved and spinel solid phases formed when the brick interacted with iron smelting slag. These phenomena, as well as the calculated lower viscosity, may lead to much deeper penetration than that exhibited by coal slag and to more severe corrosion compared to that induced by coal slag. The thermodynamic calculations well match the experimental observations, demonstrating the efficiency of the proposed simulation model for evaluating the corrosion behavior of alumina-chromia refractory.

  10. Analyses of gating thermodynamics and effects of deletions in the mechanosensitive channel TREK-1: comparisons with structural models.

    PubMed

    Maksaev, Grigory; Milac, Adina; Anishkin, Andriy; Guy, H Robert; Sukharev, Sergei

    2011-01-01

    TREK-1, a mechanosensitive K channel from the two-pore family (K(2)P), is involved in protective regulation of the resting potential in CNS neurons and other tissues. The structure of TREK-1 and the basis of its sensitivity to stretch and variety of lipid-soluble factors remain unknown. Using existing K channel structures as modeling templates, TREK-1 was envisioned as a two-fold symmetrical complex with the gate formed primarily by the centrally positioned TM2b helices of the second homologous repeat. Opening was modeled as a conical expansion of the barrel separating TM2b's accompanied by extension of TM2a helices with the cytoplasmic TM2a-TM1b connector. Seeking first experimental support to the models we have accomplished thermodynamic analysis of mouse TREK-1 gating and functional testing of several deletion mutants. The predicted increase of the channel in-plane area (ΔA) of ~5 nm(2) in models was supported by the experimental ΔA of ~4 nm(2) derived from the slope of open probability versus membrane tension in HEK-293T cells and their cytoskeleton-depleted blebs. In response to steps of suction, wild-type channel produced transient currents in cell-attached patches and mostly sustained currents upon patch excision. TREK-1 motifs not present in canonical K channels include divergent cytoplasmic N- and C-termini, and a characteristic 50-residue extracellular loop in the first homologous repeat. Deletion of the extracellular loop (Δ76-124) reduced the average current density in patches, increased spontaneous activity and generated a larger sub-population of high-conductance channels, while activation by tension augmented by arachidonic acid was fully retained. Further deletion of the C-terminal end (Δ76-124/Δ334-411) removed voltage dependency but otherwise produced no additional effect. In an attempt to generate a cysteine-free version of the channel, we mutated two remaining cysteines 159 and 219 in the transmembrane region. C219A did not compromise

  11. The effects of isomerism on the vibrational spectra and thermodynamic characteristics of biuret in the gas phase

    NASA Astrophysics Data System (ADS)

    Korolevich, M. V.; Lastochkina, V. A.; Frenkel, M. L.; Kabo, G. Ya.; Zhbankov, R. G.

    1991-03-01

    A theoretical study of the IR spectra of cis- and trans-isomers of biuret, based on coupled calculations of vibrational frequencies as a valence force field approximation and of absorption band intensities by the CNDO/2 method, is reported. Calculated thermodynamic functions for biuret agreed with experimental thermochemical data. For calculating the vibrations of an isolated biuret molecule, the experimental vapour-phase IR absorption spectra were used.

  12. Experiments on the effects of external periodic variation of constraints on the thermodynamics of an oscillatory system

    NASA Astrophysics Data System (ADS)

    Lazar, James G.; Ross, John

    1990-03-01

    The first experiments are presented which show that an external periodic perturbation imposed on a nonlinear isothermal biochemical reaction far from equilibrium may change the dissipation and hence the efficiency of that reaction; the results confirm earlier theoretical and numerical predictions. The reaction is driven and maintained far from equilibrium, a process thermodynamically equivalent to the establishment and maintenance of a concentration gradient across a membrane, i.e., a biochemical pump. We study the highly nonlinear oxidation of NADH catalyzed by the enzyme horseradish peroxidase (HRP) under conditions of continuous oxygen influx. NAD+ is recycled to NADH by a second enzymatic reaction. Experimental conditions are set so that the (HRP) reaction is in a stable limit cycle (autonomous oscillations). We then apply a periodic perturbation to the oxygen influx such that the average influx during the perturbation equals the previous steady influx. We present data obtained for a variety of frequencies and amplitudes of sinusoidal variations in the oxygen influx. Upon imposition of the periodic perturbation, we find changes in the average steady-state concentration of NADH, the average ΔG of the (HRP) reaction, the average rate of the (HRP) reaction, the phase difference between ΔG and the rate, the response of the system to the perturbation, and the dissipation of the reaction. Changes in dissipation which occur upon the imposition of an external periodic perturbation are a result of a combination of changes which occur in the thermodynamic quantities listed. These results confirm the possibility of variable efficiency of biological pumps since the establishment and maintenance of a chemical potential difference across a membrane is thermodynamically equivalent to the establishment and maintenance of a nonequilibrium stationary state in a single phase, open, homogeneous system. Moreover, the results confirm the possibility of an alternating current

  13. Thermodynamics of Bioreactions.

    PubMed

    Held, Christoph; Sadowski, Gabriele

    2016-06-07

    Thermodynamic principles have been applied to enzyme-catalyzed reactions since the beginning of the 1930s in an attempt to understand metabolic pathways. Currently, thermodynamics is also applied to the design and analysis of biotechnological processes. The key thermodynamic quantity is the Gibbs energy of reaction, which must be negative for a reaction to occur spontaneously. However, the application of thermodynamic feasibility studies sometimes yields positive Gibbs energies of reaction even for reactions that are known to occur spontaneously, such as glycolysis. This article reviews the application of thermodynamics in enzyme-catalyzed reactions. It summarizes the basic thermodynamic relationships used for describing the Gibbs energy of reaction and also refers to the nonuniform application of these relationships in the literature. The review summarizes state-of-the-art approaches that describe the influence of temperature, pH, electrolytes, solvents, and concentrations of reacting agents on the Gibbs energy of reaction and, therefore, on the feasibility and yield of biological reactions.

  14. Stochastic Thermodynamics of Learning

    NASA Astrophysics Data System (ADS)

    Goldt, Sebastian; Seifert, Udo

    2017-01-01

    Virtually every organism gathers information about its noisy environment and builds models from those data, mostly using neural networks. Here, we use stochastic thermodynamics to analyze the learning of a classification rule by a neural network. We show that the information acquired by the network is bounded by the thermodynamic cost of learning and introduce a learning efficiency η ≤1 . We discuss the conditions for optimal learning and analyze Hebbian learning in the thermodynamic limit.

  15. High-temperature thermodynamics.

    NASA Technical Reports Server (NTRS)

    Margrave, J. L.

    1967-01-01

    High temperature thermodynamics requiring species and phases identification, crystal structures, molecular geometries and vibrational, rotational and electronic energy levels and equilibrium constants

  16. Substituent effects in cation-π interactions revisited: a general approach based on intrinsic properties of the arenes.

    PubMed

    Bauzá, A; Deyà, P M; Frontera, A; Quiñonero, D

    2014-01-28

    The controversial proposal that substituent effects in cation-π interactions can be attributed mainly to electrostatic effects between the ion and local dipoles has been theoretically studied by analyzing 171 aromatics interacting with Na(+). Our results stress the importance of both electrostatic and π-polarization effects to properly describe cation-π interactions.

  17. Revisiting Lepton Flavor Universality in B Decays.

    PubMed

    Feruglio, Ferruccio; Paradisi, Paride; Pattori, Andrea

    2017-01-06

    Lepton flavor universality (LFU) in B decays is revisited by considering a class of semileptonic operators defined at a scale Λ above the electroweak scale v. The importance of quantum effects, so far neglected in the literature, is emphasized. We construct the low-energy effective Lagrangian taking into account the running effects from Λ down to v through the one-loop renormalization group equations (RGEs) in the limit of exact electroweak symmetry and QED RGEs from v down to the 1 GeV scale. The most important quantum effects turn out to be the modification of the leptonic couplings of the vector boson Z and the generation of a purely leptonic effective Lagrangian. Large LFU breaking effects in Z and τ decays and visible lepton flavor violating effects in the processes τ→μℓℓ, τ→μρ, τ→μπ, and τ→μη^{(')} are induced.

  18. Revisiting Lepton Flavor Universality in B Decays

    NASA Astrophysics Data System (ADS)

    Feruglio, Ferruccio; Paradisi, Paride; Pattori, Andrea

    2017-01-01

    Lepton flavor universality (LFU) in B decays is revisited by considering a class of semileptonic operators defined at a scale Λ above the electroweak scale v . The importance of quantum effects, so far neglected in the literature, is emphasized. We construct the low-energy effective Lagrangian taking into account the running effects from Λ down to v through the one-loop renormalization group equations (RGEs) in the limit of exact electroweak symmetry and QED RGEs from v down to the 1 GeV scale. The most important quantum effects turn out to be the modification of the leptonic couplings of the vector boson Z and the generation of a purely leptonic effective Lagrangian. Large LFU breaking effects in Z and τ decays and visible lepton flavor violating effects in the processes τ →μ ℓℓ, τ →μ ρ , τ →μ π , and τ →μ η(') are induced.

  19. Black hole thermodynamics in MOdified Gravity (MOG)

    NASA Astrophysics Data System (ADS)

    Mureika, Jonas R.; Moffat, John W.; Faizal, Mir

    2016-06-01

    We analyze the thermodynamical properties of black holes in a modified theory of gravity, which was initially proposed to obtain correct dynamics of galaxies and galaxy clusters without dark matter. The thermodynamics of non-rotating and rotating black hole solutions resembles similar solutions in Einstein-Maxwell theory with the electric charge being replaced by a new mass dependent gravitational charge Q =√{ αGN } M. This new mass dependent charge modifies the effective Newtonian constant from GN to G =GN (1 + α), and this in turn critically affects the thermodynamics of the black holes. We also investigate the thermodynamics of regular solutions, and explore the limiting case when no horizons forms. So, it is possible that the modified gravity can lead to the absence of black hole horizons in our universe. Finally, we analyze corrections to the thermodynamics of a non-rotating black hole and obtain the usual logarithmic correction term.

  20. Thermodynamics of anisotropic branes

    NASA Astrophysics Data System (ADS)

    Ávila, Daniel; Fernández, Daniel; Patiño, Leonardo; Trancanelli, Diego

    2016-11-01

    We study the thermodynamics of flavor D7-branes embedded in an anisotropic black brane solution of type IIB supergravity. The flavor branes undergo a phase transition between a `Minkowski embedding', in which they lie outside of the horizon, and a `black hole embedding', in which they fall into the horizon. This transition depends on the black hole temperature, its degree of anisotropy, and the mass of the flavor degrees of freedom. It happens either at a critical temperature or at a critical anisotropy. A general lesson we learn from this analysis is that the anisotropy, in this particular realization, induces similar effects as the temperature. In particular, increasing the anisotropy bends the branes more and more into the horizon. Moreover, we observe that the transition becomes smoother for higher anisotropies.

  1. Thermodynamics of the Earth

    NASA Astrophysics Data System (ADS)

    Stacey, Frank D.

    2010-04-01

    Applications of elementary thermodynamic principles to the dynamics of the Earth lead to robust, quantitative conclusions about the tectonic effects that arise from convection. The grand pattern of motion conveys deep heat to the surface, generating mechanical energy with a thermodynamic efficiency corresponding to that of a Carnot engine operating over the adiabatic temperature gradient between the heat source and sink. Referred to the total heat flux derived from the Earth's silicate mantle, the efficiency is 24% and the power generated, 7.7 × 1012 W, causes all the material deformation apparent as plate tectonics and the consequent geological processes. About 3.5% of this is released in seismic zones but little more than 0.2% as seismic waves. Even major earthquakes are only localized hiccups in this motion. Complications that arise from mineral phase transitions can be used to illuminate details of the motion. There are two superimposed patterns of convection, plate subduction and deep mantle plumes, driven by sources of buoyancy, negative and positive respectively, at the top and bottom of the mantle. The patterns of motion are controlled by the viscosity contrasts (>104 : 1) at these boundaries and are self-selected as the least dissipative mechanisms of heat transfer for convection in a body with very strong viscosity variation. Both are subjects of the thermodynamic efficiency argument. Convection also drives the motion in the fluid outer core that generates the geomagnetic field, although in that case there is an important energy contribution by compositional separation, as light solute is rejected by the solidifying inner core and mixed into the outer core, a process referred to as compositional convection. Uncertainty persists over the core energy balance because thermal conduction is a drain on core energy that has been a subject of diverse estimates, with attendant debate over the need for radiogenic heat in the core. The geophysical approach to

  2. In-car countermeasures open window and music revisited on the real road: popular but hardly effective against driver sleepiness.

    PubMed

    Schwarz, Johanna F A; Ingre, Michael; Fors, Carina; Anund, Anna; Kecklund, Göran; Taillard, Jacques; Philip, Pierre; Åkerstedt, Torbjörn

    2012-10-01

    This study investigated the effects of two very commonly used countermeasures against driver sleepiness, opening the window and listening to music, on subjective and physiological sleepiness measures during real road driving. In total, 24 individuals participated in the study. Sixteen participants received intermittent 10-min intervals of: (i) open window (2 cm opened); and (ii) listening to music, during both day and night driving on an open motorway. Both subjective sleepiness and physiological sleepiness (blink duration) was estimated to be significantly reduced when subjects listened to music, but the effect was only minor compared with the pronounced effects of night driving and driving duration. Open window had no attenuating effect on either sleepiness measure. No significant long-term effects beyond the actual countermeasure application intervals occurred, as shown by comparison to the control group (n = 8). Thus, despite their popularity, opening the window and listening to music cannot be recommended as sole countermeasures against driver sleepiness.

  3. Effects of salt, polyethylene glycol, and locked nucleic acids on the thermodynamic stabilities of consecutive terminal adenosine mismatches in RNA duplexes.

    PubMed

    Gu, Xiaobo; Nguyen, Mai-Thao; Overacre, Abigail; Seaton, Samantha; Schroeder, Susan J

    2013-04-04

    Consecutive terminal mismatches add thermodynamic stability to RNA duplexes and occur frequently in microRNA-mRNA interactions. Accurate thermodynamic stabilities of consecutive terminal mismatches contribute to the development of specific, high-affinity siRNA therapeutics. Consecutive terminal adenosine mismatches (TAMS) are studied at different salt concentrations, with polyethylene glycol cosolutes, and with locked nucleic acid (LNA) substitutions. These measurements provide benchmarks for the application of thermodynamic predictions to different physiological or therapeutic conditions. The salt dependence for RNA duplex stability is similar for TAMS, internal loops, and Watson-Crick duplexes. A unified model for predicting the free energy of an RNA duplex with or without loops and mismatches at lower sodium concentrations is presented. The destabilizing effects of PEG 200 are larger for TAMS than internal loops or Watson-Crick duplexes, which may result from different base stacking conformations, dynamics, and water hydration. In contrast, LNA substitutions stabilize internal loops much more than TAMS. Surprisingly, the average per adenosine increase in stability for LNA substitutions in internal loops is -1.82 kcal/mol and only -0.20 kcal/mol for TAMS. The stabilities of TAMS and internal loops with LNA substitutions have similar favorable free energies. Thus, the unfavorable free energy of adenosine internal loops is largely an entropic effect. The favorable stabilities of TAMS result mainly from base stacking. The ability of RNA duplexes to form extended terminal mismatches in the absence of proteins such as argonaute and identifying the enthalpic contributions to terminal mismatch stabilities provide insight into the physical basis of microRNA-mRNA molecular recognition and specificity.

  4. Chlorination pattern effect on thermodynamic parameters and environmental degradability for C₁₀-SCCPs: Quantum chemical calculation based on virtual combinational library.

    PubMed

    Sun, Yuzhen; Pan, Wenxiao; Lin, Yuan; Fu, Jianjie; Zhang, Aiqian

    2016-01-01

    Short-chain chlorinated paraffins (SCCPs) are still controversial candidates for inclusion in the Stockholm Convention. The inherent mixture nature of SCCPs makes it rather difficult to explore their environmental behaviors. A virtual molecule library of 42,720 C10-SCCP congeners covering the full structure spectrum was constructed. We explored the structural effects on the thermodynamic parameters and environmental degradability of C10-SCCPs through semi-empirical quantum chemical calculations. The thermodynamic properties were acquired using the AM1 method, and frontier molecular orbital analysis was carried out to obtain the E(HOMO), E(LUMO) and E(LUMO)-E(HOMO) for degradability exploration at the same level. The influence of the chlorination degree (N(Cl)) on the relative stability and environmental degradation was elucidated. A novel structural descriptor, μ, was proposed to measure the dispersion of the chlorine atoms within a molecule. There were significant correlations between thermodynamic values and N(Cl), while the reported N(Cl)-dependent pollution profile of C10-SCCPs in environmental samples was basically consistent with the predicted order of formation stability of C10-SCCP congeners. In addition, isomers with large μ showed higher relative stability than those with small μ. This could be further verified by the relationship between μ and the reactivity of nucleophilic substitution and OH attack respectively. The C10-SCCP congeners with less Cl substitution and lower dispersion degree are susceptible to environmental degradation via nucleophilic substitution and hydroxyl radical attack, while direct photolysis of C10-SCCP congeners cannot readily occur due to the large E(LUMO)-E(HOMO) values. The chlorination effect and the conclusions were further checked with appropriate density functional theory (DFT) calculations.

  5. Thermodynamic Description of Synergy in Solvent Extraction: I. Enthalpy of Mixing at the Origin of Synergistic Aggregation.

    PubMed

    Rey, J; Dourdain, S; Dufrêche, J-F; Berthon, L; Muller, J M; Pellet-Rostaing, S; Zemb, T

    2016-12-13

    Revisiting aggregation of extractant molecules into water-poor mixed reverse micelles, we propose in this paper to identify the thermodynamic origins of synergy in solvent extraction. Considering that synergistic extraction properties of a mixture of extractants is related to synergistic aggregation of this mixture, we identify here the elements at the origin of synergy by independently investigating the effect of water, acid, and extracted cations. Thermodynamic equations are proposed to describe synergistic aggregation in the peculiar case of synergistic solvent extraction by evaluating critical aggregation concentration (CAC) as well as specific interactions between extractants due to the presence of water, acid and cations. Distribution of two extractant molecules in the free extractants and in reverse micelles was assessed, leading to an estimation of the in-plane interaction parameter between extractants in the aggregates as introduced by Bergström and Eriksson ( Bergström, M.; Eriksson, J. C. A Theoretical Analysis of Synergistic Effects in Mixed Surfactant Systems . Langmuir 2000 , 16 , 7173 - 7181 ). Based on this model, we study the N,N'-dimethyl-N,N'-dioctylhexylethoxymalonamide (DMDOHEMA) and di(2-ethylexyl) phosphoric acid (HDEHP) mixture and show that adding nitric acid enhances synergistic aggregation at the equimolar ratio of the two extractants and that this configuration can be related to a favored enthalpy of mixing.

  6. The Effect of Head Orientation on Perceived Gaze Direction: Revisiting Gibson and Pick (1963) and Cline (1967)

    PubMed Central

    Moors, Pieter; Verfaillie, Karl; Daems, Thalia; Pomianowska, Iwona; Germeys, Filip

    2016-01-01

    Two biases in perceived gaze direction have been observed when eye and head orientation are not aligned. An overshoot effect indicates that perceived gaze direction is shifted away from head orientation (i.e., a repulsive effect), whereas a towing effect indicates that perceived gaze direction falls in between head and eye orientation (i.e., an attraction effect). In the 60s, three influential papers have been published with respect to the effect of head orientation on perceived gaze direction (Gibson and Pick, 1963; Cline, 1967; Anstis et al., 1969). Throughout the years, the results of two of these (Gibson and Pick, 1963; Cline, 1967) have been interpreted differently by a number of authors. In this paper, we critically discuss potential sources of confusion that have led to differential interpretations of both studies. At first sight, the results of Cline (1967), despite having been a major topic of discussion, unambiguously seem to indicate a towing effect whereas Gibson and Pick’s (1963) results seem to be the most ambiguous, although they have never been questioned in the literature. To shed further light on this apparent inconsistency, we repeated the critical experiments reported in both studies. Our results indicate an overshoot effect in both studies. PMID:27559325

  7. Atomistic Calculations of the Effect of Minor Actinides on Thermodynamic and Kinetic Properties of UO{sub 2{+-}x}

    SciTech Connect

    Deo, Chaitanya; Adnersson, Davis; Battaile, Corbett; uberuaga, Blas

    2012-10-30

    The team will examine how the incorporation of actinide species important for mixed oxide (MOX) and other advanced fuel designs impacts thermodynamic quantities of the host UO{sub 2} nuclear fuel and how Pu, Np, Cm and Am influence oxygen mobility. In many cases, the experimental data is either insufficient or missing. For example, in the case of pure NpO2, there is essentially no experimental data on the hyperstoichiometric form it is not even known if hyperstoichiometry NpO{sub 2{+-}x} is stable. The team will employ atomistic modeling tools to calculate these quantities

  8. Hold-up volume and its application in estimating effective phase ratio and thermodynamic parameters on a polysaccharide-coated chiral stationary phase.

    PubMed

    Lao, Wenjian; Gan, Jay

    2007-11-01

    As an "unretained" marker, 1,3,5-tri-tert-butylbenzene (TTBB) has been commonly used to measure the hold-up volume. Despite many racemates have been resolved on Chiralcel OJ column, the hold-up volume of the column is still not well characterized. The aim of this work was to evaluate the chromatographic behavior of TTBB on the OJ column, and its application in estimating the effective phase ratio and thermodynamic parameters. The hold-up volume was affected not only by the mobile phase composition but also the solvents used for dissolving TTBB. A higher concentration of TTBB (0.500 mg/mL) showed a better reproducibility than when used at a lower concentration. After correction for thermal expansion of the mobile phase, TTBB was found to have slight retention on the OJ phase. The effective phase ratio increased with an increase in the temperature and decrease in the strength of the mobile phase. The enthalpy and entropy of enantiomers of imidazolinone herbicides were independent of the temperature in a linear van't Hoff plot when the effective phase ratio was changed. This study shows that, based on the hold-up volume from TTBB, thermodynamic evaluation with parameters derived from the distribution constant is valuable for understanding chromatographic retention and enantioseparation mechanisms of chiral analytes.

  9. Revisiting the therapeutic effect of rTMS on negative symptoms in schizophrenia: A meta-analysis

    PubMed Central

    Shi, Chuan; Yu, Xin; Cheung, Eric F.C.; Shum, David H.K.; Chan, Raymond C.K.

    2014-01-01

    This study sought to determine the moderators in the treatment effect of repetitive transcranial magnetic stimulation (rTMS) on negative symptoms in schizophrenia. We performed a meta-analysis of prospective studies on the therapeutic application of rTMS in schizophrenia assessing the effects of both low-frequency and high-frequency rTMS on negative symptoms. Results indicate that rTMS is effective in alleviating negative symptoms in schizophrenia. The effect size was moderate (0.63 and 0.53, respectively). The effect size of rTMS on negative symptoms in sham-controlled trials was 0.80 as measured by the SANS and 0.41 as measured by the PANSS. A longer duration of illness was associated with poorer efficacy of rTMS on negative symptoms. A 10 Hz setting, at least 3 consecutive weeks of treatment, treatment site at the left dorsolateral prefrontal cortex (DLPFC) and a 110% motor threshold (MT) were found to be the best rTMS parameters for the treatment of negative symptoms. The results of our meta-analysis suggest that rTMS is an effective treatment option for negative symptoms in schizophrenia. The moderators of rTMS on negative symptoms included duration of illness, stimulus frequency, duration of illness, position and intensity of treatment as well as the type of outcome measures used. PMID:24411074

  10. Thermodynamics and combustion modeling

    NASA Technical Reports Server (NTRS)

    Zeleznik, Frank J.

    1986-01-01

    Modeling fluid phase phenomena blends the conservation equations of continuum mechanics with the property equations of thermodynamics. The thermodynamic contribution becomes especially important when the phenomena involve chemical reactions as they do in combustion systems. The successful study of combustion processes requires (1) the availability of accurate thermodynamic properties for both the reactants and the products of reaction and (2) the computational capabilities to use the properties. A discussion is given of some aspects of the problem of estimating accurate thermodynamic properties both for reactants and products of reaction. Also, some examples of the use of thermodynamic properties for modeling chemically reacting systems are presented. These examples include one-dimensional flow systems and the internal combustion engine.

  11. Revisiting caspases in sepsis

    PubMed Central

    Aziz, M; Jacob, A; Wang, P

    2014-01-01

    Sepsis is a life-threatening illness that occurs due to an abnormal host immune network which extends through the initial widespread and overwhelming inflammation, and culminates at the late stage of immunosupression. Recently, interest has been shifted toward therapies aimed at reversing the accompanying periods of immune suppression. Studies in experimental animals and critically ill patients have demonstrated that increased apoptosis of lymphoid organs and some parenchymal tissues contributes to this immune suppression, anergy and organ dysfunction. Immediate to the discoveries of the intracellular proteases, caspases for the induction of apoptosis and inflammation, and their striking roles in sepsis have been focused elaborately in a number of original and review articles. Here we revisited the different aspects of caspases in terms of apoptosis, pyroptosis, necroptosis and inflammation and focused their links in sepsis by reviewing several recent findings. In addition, we have documented striking perspectives which not only rewrite the pathophysiology, but also modernize our understanding for developing novel therapeutics against sepsis. PMID:25412304

  12. Searle's"Dualism Revisited"

    SciTech Connect

    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.

  13. Twin Signature Schemes, Revisited

    NASA Astrophysics Data System (ADS)

    Schäge, Sven

    In this paper, we revisit the twin signature scheme by Naccache, Pointcheval and Stern from CCS 2001 that is secure under the Strong RSA (SRSA) assumption and improve its efficiency in several ways. First, we present a new twin signature scheme that is based on the Strong Diffie-Hellman (SDH) assumption in bilinear groups and allows for very short signatures and key material. A big advantage of this scheme is that, in contrast to the original scheme, it does not require a computationally expensive function for mapping messages to primes. We prove this new scheme secure under adaptive chosen message attacks. Second, we present a modification that allows to significantly increase efficiency when signing long messages. This construction uses collision-resistant hash functions as its basis. As a result, our improvements make the signature length independent of the message size. Our construction deviates from the standard hash-and-sign approach in which the hash value of the message is signed in place of the message itself. We show that in the case of twin signatures, one can exploit the properties of the hash function as an integral part of the signature scheme. This improvement can be applied to both the SRSA based and SDH based twin signature scheme.

  14. The Effects of Precautionary Messages about Electromagnetic Fields from Mobile Phones and Base Stations Revisited: The Role of Recipient Characteristics.

    PubMed

    Boehmert, Christoph; Wiedemann, Peter; Pye, Jonathon; Croft, Rodney

    2016-05-10

    Precautionary messages have been shown to increase recipients' threat perceptions about radio-frequency electromagnetic fields (RF-EMFs) emitted by mobile phones and mobile phone base stations. The current study explored the interplay of variables on the side of message recipients with this effect. The individual difference variables of interest were gender, trait anxiety, personal need for structure, and personal fear of invalidity. Furthermore, the study determined whether the increased threat perception is accompanied by emotional distress. A total of 298 university students answered a survey after reading either a basic text about RF-EMFs or a text including precautionary information. Linear multiple regression with interactions analyses showed that the effect of precautionary messages differed for people with different levels of trait anxiety. How trait anxiety was related to the effect of precautionary messages in turn depended on participants' gender. Personal need for structure and personal fear of invalidity were mostly unrelated to the effect of precautionary messages. Regarding participants' emotional distress, we found no difference in state anxiety scores between those participants who received precautionary information and those who did not. The findings show that the effects of precautionary messages on threat perception depend on individual difference variables such as recipients' trait anxiety and gender. Also, the fact that precautionary communication did not result in heightened state anxiety challenges the assumption that precautionary messages induce fear or anxiety.

  15. Association thermodynamics and conformational stability of beta-sheet amyloid beta(17-42) oligomers: effects of E22Q (Dutch) mutation and charge neutralization.

    PubMed

    Blinov, Nikolay; Dorosh, Lyudmyla; Wishart, David; Kovalenko, Andriy

    2010-01-20

    Amyloid fibrils are associated with many neurodegenerative diseases. It was found that amyloidogenic oligomers, not mature fibrils, are neurotoxic agents related to these diseases. Molecular mechanisms of infectivity, pathways of aggregation, and molecular structure of these oligomers remain elusive. Here, we use all-atom molecular dynamics, molecular mechanics combined with solvation analysis by statistical-mechanical, three-dimensional molecular theory of solvation (also known as 3D-RISM-KH) in a new MM-3D-RISM-KH method to study conformational stability, and association thermodynamics of small wild-type Abeta(17-42) oligomers with different protonation states of Glu(22), as well the E22Q (Dutch) mutants. The association free energy of small beta-sheet oligomers shows near-linear trend with the dimers being thermodynamically more stable relative to the larger constructs. The linear (within statistical uncertainty) dependence of the association free energy on complex size is a consequence of the unilateral stacking of monomers in the beta-sheet oligomers. The charge reduction of the wild-type Abeta(17-42) oligomers upon protonation of the solvent-exposed Glu(22) at acidic conditions results in lowering the association free energy compared to the wild-type oligomers at neutral pH and the E22Q mutants. The neutralization of the peptides because of the E22Q mutation only marginally affects the association free energy, with the reduction of the direct electrostatic interactions mostly compensated by the unfavorable electrostatic solvation effects. For the wild-type oligomers at acidic conditions such compensation is not complete, and the electrostatic interactions, along with the gas-phase nonpolar energetic and the overall entropic effects, contribute to the lowering of the association free energy. The differences in the association thermodynamics between the wild-type Abeta(17-42) oligomers at neutral pH and the Dutch mutants, on the one hand, and the Abeta(17

  16. Sex Offender Recidivism Revisited: Review of Recent Meta-analyses on the Effects of Sex Offender Treatment.

    PubMed

    Kim, Bitna; Benekos, Peter J; Merlo, Alida V

    2016-01-01

    The effectiveness of sex offender treatment programs continues to generate misinformation and disagreement. Some literature reviews conclude that treatment does not reduce recidivism while others suggest that specific types of treatment may warrant optimism. The principal purpose of this study is to update the most recent meta-analyses of sex offender treatments and to compare the findings with an earlier study that reviewed the meta-analytic studies published from 1995 to 2002. More importantly, this study examines effect sizes across different age populations and effect sizes across various sex offender treatments. Results of this review of meta-analyses suggest that sex offender treatments can be considered as "proven" or at least "promising," while age of participants and intervention type may influence the success of treatment for sex offenders. The implications of these findings include achieving a broader understanding of intervention moderators, applying such interventions to juvenile and adult offenders, and outlining future areas of research.

  17. Thermodynamic power of non-Markovianity

    PubMed Central

    Bylicka, Bogna; Tukiainen, Mikko; Chruściński, Dariusz; Piilo, Jyrki; Maniscalco, Sabrina

    2016-01-01

    The natural framework to discuss thermodynamics at the quantum level is the theory of open quantum systems. Memory effects arising from strong system-environment correlations may lead to information back-flow, that is non-Markovian behaviour. The relation between non-Markovianity and quantum thermodynamics has been until now largely unexplored. Here we show by means of Landauer’s principle that memory effects control the amount of work extraction by erasure in presence of realistic environments. PMID:27323947

  18. The Role of Socioeconomic Status and School Quality in the Philippines: Revisiting the Heyneman-Loxley Effect

    ERIC Educational Resources Information Center

    Huang, Francis L.

    2010-01-01

    In 1983, Heyneman and Loxley stated that in low income countries, school-level factors could account for a greater proportion of variance in student achievement as compared to student-level characteristics. The phenomenon has come to be known as the "HL effect" and signaled the important role of schools in developing countries. This…

  19. Effects of Familiarity on the Perceptual Integrality of the Identity and Expression of Faces: The Parallel-Route Hypothesis Revisited

    ERIC Educational Resources Information Center

    Ganel, Tzvi; Goshen-Gottstein, Yonatan

    2004-01-01

    The effects of familiarity on selective attention for the identity and expression of faces were tested using Garner's speeded-classification task. In 2 experiments, participants classified expression (or identity) of familiar and unfamiliar faces while the irrelevant dimension of identity (or expression) was either held constant (baseline…

  20. Nature of Interactions during Teacher-Student Writing Conferences, Revisiting the Potential Effects of Self-Efficacy Beliefs

    ERIC Educational Resources Information Center

    Bayraktar, Aysegül

    2013-01-01

    Problem Statement: Within Language Arts instruction the use of teacher-student writing conferences is accepted as an effective strategy for teaching writing. The writing conference allows for an individual one-on-one teacher-student conversation about the students' writing or writing process and provides the student an audience in terms of…

  1. Revisiting the health effects of psychological stress—its influence on susceptibility to ionizing radiation: a mini-review

    PubMed Central

    Wang, Bing; Katsube, Takanori; Begum, Nasrin; Nenoi, Mitsuru

    2016-01-01

    Both psychological stress (PS) and ionizing radiation (IR) cause varied detrimental effects on humans. There has been no direct evidence so far showing PS alone could cause cancer; however, long-lasting PS may affect our overall health and ability to cope with cancer. Due to their living conditions and occupations, some people may encounter concurrent exposure to both PS and IR to a high extent. In addition to possible health effects resulting directly from exposure to IR on these people, fear of IR exposure is also a cause of PS. The question of whether PS would influence susceptibility to IR, radiocarcinogenesis in particular, is of great concern by both the academic world and the public. Recently, investigations using animal PS models demonstrated that PS could modulate susceptibility to IR, causing increased susceptibility to radiocarcinogenesis in Trp53-heterozygous mice, hematological toxicity in peripheral blood and elevated chromosome aberration (dicentrics) frequency in splenocytes of Trp53–wild-type mice. To actively reduce health risk from exposure to IR, further studies are needed to cumulate more evidence and provide insights into the mechanisms underlying the alterations in susceptibility due to PS modulation. This mini-review gives a general overview of the significance of PS effects on humans and experimental animals, with a special focus on summarizing the latest weight-of-evidence approaches to radiobiological studies on PS-induced alterations in susceptibility in experimental animal models. The susceptibility being investigated is mainly in the context of the impact of the modulatory effect of PS on radiocarcinogenesis; we seek to improve understanding of the combined effects of exposure to both PS and IR in order to facilitate, via active intervention, strategies for radiation risk reduction. PMID:27242342

  2. Benjamin Franklin and Mesmerism, revisited.

    PubMed

    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.

  3. Cultural Warping of Childbirth, Revisited

    PubMed Central

    Budin, Wendy C.

    2007-01-01

    In this column, the editor of The Journal of Perinatal Education revisits Doris Haire's classic 1972 article, “The Cultural Warping of Childbirth,” and describes the birth culture of today. The editor also describes the contents of this issue, which offer a broad range of resources, research, and inspiration for childbirth educators in their efforts to promote normal birth.

  4. The "Mushroom Cloud" Demonstration Revisited

    ERIC Educational Resources Information Center

    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…

  5. The role of eye movements in the missing-letter effect revisited with the rapid serial visual presentation procedure.

    PubMed

    Saint-Aubin, Jean; Kenny, Sophie; Roy-Charland, Annie

    2010-03-01

    When participants read a text while searching for a target letter, they are more likely to miss the target letter embedded in frequent function words than in less frequent content words. This effect is usually observed with a text displayed normally, for which it has been found that frequent function words are fixated for a smaller amount of time than less frequent content words. However, similar pattern of omissions have been observed with a rapid serial visual presentation procedure in which words appear one at a time. These parallel results would demonstrate that fixation duration per se is not the proximal cause of the missing-letter effect only if eye movements are not made during the rapid serial visual presentation procedure. Therefore, the authors performed eye monitoring during the rapid serial visual presentation procedure. Results revealed that, with a rapid serial visual presentation procedure, participants fixated function and content words for almost the entire presentation duration. It is concluded that eye movements are not the proximal cause of the missing-letter effect.

  6. Thermodynamic laws apply to brain function.

    PubMed

    Salerian, Alen J

    2010-02-01

    Thermodynamic laws and complex system dynamics govern brain function. Thus, any change in brain homeostasis by an alteration in brain temperature, neurotransmission or content may cause region-specific brain dysfunction. This is the premise for the Salerian Theory of Brain built upon a new paradigm for neuropsychiatric disorders: the governing influence of neuroanatomy, neurophysiology, thermodynamic laws. The principles of region-specific brain function thermodynamics are reviewed. The clinical and supporting evidence including the paradoxical effects of various agents that alter brain homeostasis is demonstrated.

  7. A potential role for isothermal calorimetry in studies of the effects of thermodynamic non-ideality in enzyme-catalyzed reactions.

    PubMed

    Lonhienne, Thierry G A; Winzor, Donald J

    2004-01-01

    Attention is drawn to the feasibility of using isothermal calorimetry for the characterization of enzyme reactions under conditions bearing greater relevance to the crowded biological environment, where kinetic parameters are likely to differ significantly from those obtained by classical enzyme kinetic studies in dilute solution. An outline of the application of isothermal calorimetry to the determination of enzyme kinetic parameters is followed by considerations of the nature and consequences of crowding effects in enzyme catalysis. Some of those effects of thermodynamic non-ideality are then illustrated by means of experimental results from calorimetric studies of the effect of molecular crowding on the kinetics of catalysis by rabbit muscle pyruvate kinase. This review concludes with a discussion of the potential of isothermal calorimetry for the experimental determination of kinetic parameters for enzymes either in biological environments or at least in media that should provide reasonable approximations of the crowded conditions encountered in vivo.

  8. Revisiting the effects of self-protective behaviors on the risk of injury in assaults against women.

    PubMed

    Yun, Ilhong; Lee, Julak

    2014-01-01

    Using data from the National Crime Victimization Survey (NCVS; 1992-2005), we closely examined the effects of victims' self-protective actions on the risk of injury among female nonsexual assault victims. Building on previous research, we focused on 3 important methodological and conceptual issues: (a) gradational coding of the 16 different NCVS self-protective actions, (b) separate analyses of serious injuries, and (c) the victim-offender relationship. Our analyses demonstrated that the risk of injury was strongly and positively associated with the degree of forcefulness of self-protective actions. Furthermore, the likelihood of victim injury was inversely related to the relational distance between the victim and the offender.

  9. The effective atomic number revisited in the light of modern photon-interaction cross-section databases.

    PubMed

    Manohara, S R; Hanagodimath, S M; Thind, K S; Gerward, L

    2010-01-01

    The effective atomic number, Z(eff), has been calculated for fatty acids and cysteine. It is shown that Z(eff) is a useful parameter for low-Z materials at any energy above 1 keV. Absorption edges of medium-Z elements may complicate the energy dependence of Z(eff) below 10 keV. The notion of Z(eff) is perhaps most useful at energies where Compton scattering is dominating, and where Z(eff) is equal to the mean atomic number, Z, over a wide energy range around 1 MeV.

  10. AC-Susceptibility and Ultrasonic Attenuation Measurements of Vortex Dynamics in the Vicinity of the Peak Effect in V-Ti Alloys - Multicriticality Revisited

    NASA Astrophysics Data System (ADS)

    Dimitrov, I. K.

    2005-03-01

    In-situ SANS and ac-susceptibility measurements have provided evidence for a first-order Bragg glass transition into a disordered vortex state in a Nb single crystal. This transition manifests itself in the peak effect (PE) in the critical current density, widely believed to be associated with the sudden softening of the vortex lattice. Subsequent studies mapping the full phase diagram in the same sample have suggested the existence of four distinct phase boundaries meeting at a single multicritical point (MCP). The natures of the transition lines combined with simple thermodynamic requirements suggest that the MCP is a bicritical point. This would rule out either the bulk transition line Tc2(T) or the surface superconducting transition Hc3(T) as being related to the MCP. Mutual inductance magnetic ac-susceptibility and ultrasonic attenuation measurements in V-21at.%Ti have unequivocally established the presence of a PE in this alloy. The H-T phase diagram for this sample will be presented and vortex dynamics in the vicinity of the PE will be discussed. We are indebted to Prof. Shapira of Tufts University for providing us with the sample. This work was supported by the NSF under Grant No. DMR-0406626.

  11. Stories to Make Thermodynamics and Related Subjects More Palatable

    NASA Astrophysics Data System (ADS)

    Bartell, Lawrence S.

    2001-08-01

    A collection of vignettes either recounting the personalities of some of the architects of thermodynamics or noting steps and missteps in the development of thermodynamics and the kinetic theory is combined with a set of stories illustrating thermodynamic principles. These offerings turned out to be much more easily remembered by students and were more effective in conveying certain points than a direct, unadorned exposition of thermodynamic laws and applications. For one thing, the stories kept the students awake and receptive to ideas. Students had invariably entered the class having heard horror stories about how tedious and impossibly difficult thermodynamics courses are.

  12. Does the Kuleshov Effect Really Exist? Revisiting a Classic Film Experiment on Facial Expressions and Emotional Contexts.

    PubMed

    Barratt, Daniel; Rédei, Anna Cabak; Innes-Ker, Åse; van de Weijer, Joost

    2016-08-01

    According to film mythology, the Soviet filmmaker Lev Kuleshov conducted an experiment in which he combined a close-up of an actor's neutral face with three different emotional contexts: happiness, sadness, and hunger. The viewers of the three film sequences reportedly perceived the actor's face as expressing an emotion congruent with the given context. It is not clear, however, whether or not the so-called "Kuleshov effect" really exists. The original film footage is lost and recent attempts at replication have produced either conflicting or unreliable results. The current paper describes an attempt to replicate Kuleshov's original experiment using an improved experimental design. In a behavioral and eye tracking study, 36 participants were each presented with 24 film sequences of neutral faces across six emotional conditions. For each film sequence, the participants were asked to evaluate the emotion of the target person in terms of valence, arousal, and category. The participants' eye movements were recorded throughout. The results suggest that some sort of Kuleshov effect does in fact exist. For each emotional condition, the participants tended to choose the appropriate category more frequently than the alternative options, while the answers to the valence and arousal questions also went in the expected directions. The eye tracking data showed how the participants attended to different regions of the target person's face (in light of the intermediate context), but did not reveal the expected differences between the emotional conditions.

  13. Aptitude-treatment interactions revisited: effect of metacognitive intervention on subtypes of written expression in elementary school students.

    PubMed

    Hooper, Stephen R; Wakely, Melissa B; de Kruif, Renee E L; Swartz, Carl W

    2006-01-01

    We examined the effectiveness of a metacognitive intervention for written language performance, based on the Hayes model of written expression, for 73 fourth-grade (n = 38) and fifth-grade (n = 35) students. The intervention consisted of twenty 45-min writing lessons designed to improve their awareness of writing as a problem-solving process. Each of the lessons addressed some aspect of planning, translating, and reflecting on written products; their self-regulation of these processes; and actual writing practice. All instruction was conducted in intact classrooms. Prior to the intervention, all students received a battery of neurocognitive tests measuring executive functions, attention, and language. In addition, preintervention writing samples were obtained and analyzed holistically and for errors in syntax, semantics, and spelling. Following the intervention, the writing tasks were readministered and cluster analysis of the neurocognitive data was conducted. Cluster analytic procedures yielded 7 reliable clusters: 4 normal variants, 1 Problem Solving weakness, 1 Problem Solving Language weaknesses, and 1 Problem Solving strength. The response to the single treatment by these various subtypes revealed positive but modest findings. Significant group differences were noted for improvement in syntax errors and spelling, with only spelling showing differential improvement for the Problem Solving Language subtype. In addition, there was a marginally significant group effect for holistic ratings. These findings provide initial evidence that Writing Aptitude (subtype) x Single Treatment interactions exist in writing, but further research is needed with other classification schemes and interventions.

  14. Effect of pH and monovalent cations on the Raman spectrum of water: Basics revisited and application to measure concentration gradients at water/solid interface in Si3N4 biomaterial

    NASA Astrophysics Data System (ADS)

    Pezzotti, Giuseppe; Puppulin, Leonardo; La Rosa, Angelo; Boffelli, Marco; Zhu, Wenliang; McEntire, Bryan J.; Hosogi, Shigekuni; Nakahari, Takashi; Marunaka, Yoshinori

    2015-12-01

    The effect of hydrogen carbonate (HCO3-) and cations (Na+, K+) solvated in water were revisited according to high spectrally resolved Raman measurements. Water solutions with different bicarbonate concentrations or added with increasing amounts of monovalent cations were examined with respect to their Raman spectra both in the bulk state and at the solid/liquid interface with a silicon nitride (Si3N4) bioceramic. Spectroscopic calibrations confirmed that the Raman emission from OH-stretching in water is sensitive to molarity variations (in the order of tens of mM). The concentration gradient developed at the solid/liquid interface in cation-added solutions interacting with a Si3N4 surface was measured and found to be peculiar to individual cations. Local variation in pH was detected in ionic solutions interacting with Si3N4 samples, which might represent a useful property for Si3N4 in a number of biomedical applications.

  15. Sensory neural pathways revisited to unravel the temporal dynamics of the Simon effect: A model-based cognitive neuroscience approach.

    PubMed

    Salzer, Yael; de Hollander, Gilles; Forstmann, Birte U

    2017-02-24

    The Simon task is one of the most prominent interference tasks and has been extensively studied in experimental psychology and cognitive neuroscience. Despite years of research, the underlying mechanism driving the phenomenon and its temporal dynamics are still disputed. Within the framework of the review, we adopt a model-based cognitive neuroscience approach. We first go over key findings in the literature of the Simon task, discuss competing qualitative cognitive theories and the difficulty of testing them empirically. We then introduce sequential sampling models, a particular class of mathematical cognitive process models. Finally, we argue that the brain architecture accountable for the processing of spatial ('where') and non-spatial ('what') information, could constrain these models. We conclude that there is a clear need to bridge neural and behavioral measures, and that mathematical cognitive models may facilitate the construction of this bridge and work towards revealing the underlying mechanisms of the Simon effect.

  16. A coarse-grained model for DNA-functionalized spherical colloids, revisited: Effective pair potential from parallel replica simulations

    NASA Astrophysics Data System (ADS)

    Theodorakis, Panagiotis E.; Dellago, Christoph; Kahl, Gerhard

    2013-01-01

    We discuss a coarse-grained model recently proposed by Starr and Sciortino [J. Phys.: Condens. Matter 18, L347 (2006), 10.1088/0953-8984/18/26/L02] for spherical particles functionalized with short single DNA strands. The model incorporates two key aspects of DNA hybridization, i.e., the specificity of binding between DNA bases and the strong directionality of hydrogen bonds. Here, we calculate the effective potential between two DNA-functionalized particles of equal size using a parallel replica protocol. We find that the transition from bonded to unbonded configurations takes place at considerably lower temperatures compared to those that were originally predicted using standard simulations in the canonical ensemble. We put particular focus on DNA-decorations of tetrahedral and octahedral symmetry, as they are promising candidates for the self-assembly into a single-component diamond structure. Increasing colloid size hinders hybridization of the DNA strands, in agreement with experimental findings.

  17. Revisiting the 'cis-effect' in 1,2-difluoro derivatives of ethylene and diazene using ab initio multireference methods

    NASA Astrophysics Data System (ADS)

    Banerjee, Debi; Ghosh, Anirban; Chattopadhyay, Sudip; Ghosh, Pradipta; Chaudhuri, Rajat K.

    2014-12-01

    The relative stabilities of cis- and trans- isomers of 1,2-difluoroethylene and 1,2-difluorodiazene have been studied via the state-specific multireference coupled cluster (SS-MRCC) method and its perturbative counterpart through the computation of the optimised structures and corresponding energies. Despite the existence of several cis-destabilising mechanisms, present calculations reveal the energetic preference of the cis- isomer (the cis-effect) for the systems considered here. Differences in structural parameters and vibrational frequencies among cis- and trans- isomers have been discussed. Very good agreement of our estimates has been found with the benchmark theoretical and experimental results. The SS-MRCC methods produce a smooth and consistent behaviour across the entire torsional surface for the cis-trans isomerisation indicating that the method has sufficient flexibility to model large changes in electronic structure that accompany chemical changes.

  18. Nutational Damping Revisited

    NASA Astrophysics Data System (ADS)

    Burns, J. A.; Sharma, I.

    2000-10-01

    Motivated by the recent detection of complex rotational states for several asteroids and comets, as well as by the ongoing and planned spacecraft missions to such bodies, which should allow their rotational states to be accurately determined, we revisit the problem of the nutational damping of small solar system bodies. The nutational damping of asteroids has been approximately analyzed by Prendergast (1958), Burns and Safronov (1973), and Efroimsky and Lazarian (2000). Many other similar dynamical studies concern planetary wobble decay (e.g., Peale 1973; Yoder and Ward 1979), interstellar dust grain alignment (e.g., Purcell 1979; Lazarian and Efroimsky 1999) and damping of Earth's Chandler wobble (Lambeck 1980). Recall that rotational energy loss for an isolated body aligns the body's angular momentum vector with its axis of maximum inertia. Assuming anelastic dissipation, simple dimensional analysis determines a functional form of the damping timescale, on which all the above authors agree. However, the numerical coefficients of published results are claimed to differ by orders of magnitude. Differences have been ascribed to absent physics, to solutions that fail to satisfy boundary conditions perfectly, and to unphysical choices for the Q parameter. The true reasons for the discrepancy are unclear since, despite contrary claims, the full 3D problem (nutational damping of an anelastic ellipsoid) is analytically intractable so far. To move the debate forward, we compare the solution of a related 2D problem to the expressions found previously, and we present results from a finite element model. On this basis, we feel that previous rates for the decay of asteroidal tumbling (Harris 1994), derived from Burns and Safronov (1973), are likely to be accurate, at least to a factor of a few. Funded by NASA.

  19. Thermodynamic Insight in the High-Pressure Behavior of UiO-66: Effect of Linker Defects and Linker Expansion

    PubMed Central

    2016-01-01

    In this Article, we present a molecular-level understanding of the experimentally observed loss of crystallinity in UiO-66-type metal–organic frameworks, including the pristine UiO-66 to -68 as well as defect-containing UiO-66 materials, under the influence of external pressure. This goal is achieved by constructing pressure-versus-volume profiles at finite temperatures using a thermodynamic approach relying on ab initio derived force fields. On the atomic level, the phenomenon is reflected in a sudden drop in the number of symmetry operators for the crystallographic unit cell because of the disordered displacement of the organic linkers with respect to the inorganic bricks. For the defect-containing samples, a reduced mechanical stability is observed, however, critically depending on the distribution of these defects throughout the material, hence demonstrating the importance of judiciously characterizing defects in these materials. PMID:27594765

  20. The effect of stereochemistry on the thermodynamic characteristics of the binding of fenoterol stereoisomers to the beta(2)-adrenoceptor.

    PubMed

    Jozwiak, Krzysztof; Toll, Lawrence; Jimenez, Lucita; Woo, Anthony Yiu-Ho; Xiao, Rui-Ping; Wainer, Irving W

    2010-06-01

    The binding thermodynamics of the stereoisomers of fenoterol, (R,R')-, (S,S')-, (R,S')-, and (S,R')-fenoterol, to the beta(2)-adrenergic receptor (beta(2)-AR) have been determined. The experiments utilized membranes obtained from HEK cells stably transfected with cDNA encoding human beta(2)-AR. Competitive displacement studies using [(3)H]CGP-12177 as the marker ligand were conducted at 4, 15, 25, 30 and 37 degrees C, the binding affinities calculated and the standard enthalpic (DeltaH degrees ) and standard entropic (DeltaS degrees ) contribution to the standard free energy change (DeltaG degrees ) associated with the binding process determined through the construction of van't Hoff plots. The results indicate that the binding of (S,S')- and (S,R')-fenoterol were predominately enthalpy-driven processes while the binding of (R,R')- and (R,S')-fenoterol were entropy-driven. All of the fenoterol stereoisomers are full agonists of the beta(2)-AR, and, therefore, the results of this study are inconsistent with the previously described "thermodynamic agonist-antagonist discrimination", in which the binding of an agonist to the beta-AR is entropy-driven and the binding of an antagonist is enthalpy-driven. In addition, the data demonstrate that the chirality of the carbon atom containing the beta-hydroxyl group of the fenoterol molecule (the beta-OH carbon) is a key factor in the determination of whether the binding process will be enthalpy-driven or entropy-driven. When the configuration at the beta-OH carbon is S the binding process is enthalpy-driven while the R configuration produces an entropy-driven process.

  1. Effect of Ni and Pd Addition on Mechanical, Thermodynamic, and Electronic Properties of AuSn4-Based Intermetallics: A Density Functional Investigation

    NASA Astrophysics Data System (ADS)

    Tian, Yali; Zhou, Wei; Wu, Ping

    2016-08-01

    The effects of Ni and Pd addition on the mechanical, thermodynamic, and electronic properties of AuSn4-based intermetallic compounds (IMCs) have been investigated by first-principles calculations to reveal the essence of Au embrittlement. Three kinds of doped (namely Ni-doped, Pd-doped, and Ni/Pd-codoped) IMCs are considered in this work. The polycrystalline elastic properties are deduced from single-crystal elastic constants. It is found that the doped systems together with nondoped AuSn4 are all ductile phases. For Ni-doped AuSn4, the modulus, hardness, brittleness, Debye temperature, and minimum thermal conductivity increase with the Ni fraction, but this is not the case for the Pd-doped material, since Au0.75Pd0.25Sn4 is the more brittle phase. For Au0.5Pd0.25Ni0.25Sn4, the mechanical, thermodynamic, and electronic properties are similar to those of Au0.5Pd0.5Sn4.

  2. Hierarchical structure of the energy landscape of proteins revisited by time series analysis. II. Investigation of explicit solvent effects

    NASA Astrophysics Data System (ADS)

    Alakent, Burak; Camurdan, Mehmet C.; Doruker, Pemra

    2005-10-01

    Time series analysis tools are employed on the principal modes obtained from the Cα trajectories from two independent molecular-dynamics simulations of α-amylase inhibitor (tendamistat). Fluctuations inside an energy minimum (intraminimum motions), transitions between minima (interminimum motions), and relaxations in different hierarchical energy levels are investigated and compared with those encountered in vacuum by using different sampling window sizes and intervals. The low-frequency low-indexed mode relationship, established in vacuum, is also encountered in water, which shows the reliability of the important dynamics information offered by principal components analysis in water. It has been shown that examining a short data collection period (100ps) may result in a high population of overdamped modes, while some of the low-frequency oscillations (<10cm-1) can be captured in water by using a longer data collection period (1200ps). Simultaneous analysis of short and long sampling window sizes gives the following picture of the effect of water on protein dynamics. Water makes the protein lose its memory: future conformations are less dependent on previous conformations due to the lowering of energy barriers in hierarchical levels of the energy landscape. In short-time dynamics (<10ps), damping factors extracted from time series model parameters are lowered. For tendamistat, the friction coefficient in the Langevin equation is found to be around 40-60cm-1 for the low-indexed modes, compatible with literature. The fact that water has increased the friction and that on the other hand has lubrication effect at first sight contradicts. However, this comes about because water enhances the transitions between minima and forces the protein to reduce its already inherent inability to maintain oscillations observed in vacuum. Some of the frequencies lower than 10cm-1 are found to be overdamped, while those higher than 20cm-1 are slightly increased. As for the long

  3. The botanist effect revisited: plant species richness, county area, and human population size in the United States.

    PubMed

    Pautasso, Marco; McKinney, Michael L

    2007-10-01

    The "botanist effect" is thought to be the reason for higher plant species richness in areas where botanists are disproportionately present as an artefactual consequence of a more thorough sampling. We examined whether this was the case for U.S. counties. We collated the number of species of vascular plants, human population size, and the area of U.S. counties. Controlling for spatial autocorrelation and county area, plant species richness increased with human population size and density in counties with and without universities and/or botanical gardens, with no significant differences in the relation between the two subsets. This is consistent with previous findings and further evidence of a broad-scale positive correlation between species richness and human population presence, which has important consequences for the experience of nature by inhabitants of densely populated regions. Combined with the many reports of a negative correlation between the two variables at a local scale, the positive relation between plant species richness in U.S. counties and human population presence stresses the need for the conservation of seminatural areas in urbanized ecosystems and for the containment of urban and suburban sprawl.

  4. Revisiting the effects of Parkinson's disease and frontal lobe lesions on task switching: the role of rule reconfiguration.

    PubMed

    Kehagia, Angie A; Barker, Roger A; Robbins, Trevor W

    2014-03-01

    flexibility. These manipulations may help decipher the differential effects of progressive neurodegeneration on parkinsonian cognition, and provide a framework in which to conceptualize the contributions of cortical and subcortical regions to cognitive control.

  5. Turbopump thermodynamic cooling

    NASA Technical Reports Server (NTRS)

    Patten, T. C.; Mckee, H. B.

    1972-01-01

    System for cooling turbopumps used in cryogenic fluid storage facilities is described. Technique uses thermodynamic propellant vent to intercept pump heat at desired conditions. Cooling system uses hydrogen from outside source or residual hydrogen from cryogenic storage tank.

  6. Thermodynamics: A Stirling effort

    NASA Astrophysics Data System (ADS)

    Horowitz, Jordan M.; Parrondo, Juan M. R.

    2012-02-01

    The realization of a single-particle Stirling engine pushes thermodynamics into stochastic territory where fluctuations dominate, and points towards a better understanding of energy transduction at the microscale.

  7. Thermodynamics and Frozen Foods.

    ERIC Educational Resources Information Center

    Kerr, William L.; Reid, David S.

    1993-01-01

    The heat content of a food at a given temperature can be described by the thermodynamic property of enthalpy. Presents a method to construct a simple calorimeter for measuring the enthalpy changes of different foods during freezing. (MDH)

  8. Electrochemical thermodynamic measurement system

    DOEpatents

    Reynier, Yvan; Yazami, Rachid; Fultz, Brent T.

    2009-09-29

    The present invention provides systems and methods for accurately characterizing thermodynamic and materials properties of electrodes and electrochemical energy storage and conversion systems. Systems and methods of the present invention are configured for simultaneously collecting a suite of measurements characterizing a plurality of interconnected electrochemical and thermodynamic parameters relating to the electrode reaction state of advancement, voltage and temperature. Enhanced sensitivity provided by the present methods and systems combined with measurement conditions that reflect thermodynamically stabilized electrode conditions allow very accurate measurement of thermodynamic parameters, including state functions such as the Gibbs free energy, enthalpy and entropy of electrode/electrochemical cell reactions, that enable prediction of important performance attributes of electrode materials and electrochemical systems, such as the energy, power density, current rate and the cycle life of an electrochemical cell.

  9. Compounding effects of fluid confinement and surface strain on the wet–dry transition, thermodynamic response, and dynamics of water–graphene systems

    DOE PAGES

    Chialvo, Ariel A.; Vlcek, Lukas; Cummings, Peter T.

    2015-01-01

    We studied the link between the water-mediated (tensile or compressive) strain-driven hydration free energy changes in the association process involving finite-size graphene surfaces, the resulting water-graphene interfacial behavior, and the combined effect of surface strain and fluid confinement on the thermodynamic response functions and the dynamics of water. In this study, we found that either small surface corrugation (compressive strain) or surface stretching (tensile strain) is able to enhance significantly the water-graphene hydrophobicity relative to that of the unstrained surface, an effect that exacerbates the confinement impact on the isothermal compressibility and isobaric thermal expansivity of confined water, as wellmore » as on the slowing down of its dynamics that gives rise to anomalous diffusivity.« less

  10. Compounding effects of fluid confinement and surface strain on the wet–dry transition, thermodynamic response, and dynamics of water–graphene systems

    SciTech Connect

    Chialvo, Ariel A.; Vlcek, Lukas; Cummings, Peter T.

    2015-01-01

    We studied the link between the water-mediated (tensile or compressive) strain-driven hydration free energy changes in the association process involving finite-size graphene surfaces, the resulting water-graphene interfacial behavior, and the combined effect of surface strain and fluid confinement on the thermodynamic response functions and the dynamics of water. In this study, we found that either small surface corrugation (compressive strain) or surface stretching (tensile strain) is able to enhance significantly the water-graphene hydrophobicity relative to that of the unstrained surface, an effect that exacerbates the confinement impact on the isothermal compressibility and isobaric thermal expansivity of confined water, as well as on the slowing down of its dynamics that gives rise to anomalous diffusivity.

  11. Thermodynamical string fragmentation

    NASA Astrophysics Data System (ADS)

    Fischer, Nadine; Sjöstrand, Torbjörn

    2017-01-01

    The observation of heavy-ion-like behaviour in pp collisions at the LHC suggests that more physics mechanisms are at play than traditionally assumed. The introduction e.g. of quark-gluon plasma or colour rope formation can describe several of the observations, but as of yet there is no established paradigm. In this article we study a few possible modifications to the Pythia event generator, which describes a wealth of data but fails for a number of recent observations. Firstly, we present a new model for generating the transverse momentum of hadrons during the string fragmentation process, inspired by thermodynamics, where heavier hadrons naturally are suppressed in rate but obtain a higher average transverse momentum. Secondly, close-packing of strings is taken into account by making the temperature or string tension environment-dependent. Thirdly, a simple model for hadron rescattering is added. The effect of these modifications is studied, individually and taken together, and compared with data mainly from the LHC. While some improvements can be noted, it turns out to be nontrivial to obtain effects as big as required, and further work is called for.

  12. Simple, Chemoselective Hydrogenation with Thermodynamic Stereocontrol

    PubMed Central

    2015-01-01

    Few methods permit the hydrogenation of alkenes to a thermodynamically favored configuration when steric effects dictate the alternative trajectory of hydrogen delivery. Dissolving metal reduction achieves this control, but with extremely low functional group tolerance. Here we demonstrate a catalytic hydrogenation of alkenes that affords the thermodynamic alkane products with remarkably broad functional group compatibility and rapid reaction rates at standard temperature and pressure. PMID:24428640

  13. Thermodynamic properties of black holes in de Sitter space

    NASA Astrophysics Data System (ADS)

    Li, Huai-Fan; Ma, Meng-Sen; Ma, Ya-Qin

    2017-01-01

    We study the thermodynamic properties of Schwarzschild-de Sitter (SdS) black hole and Reissner-Nordström-de Sitter (RNdS) black hole in view of global and effective thermodynamic quantities. Making use of the effective first law of thermodynamics, we can derive the effective thermodynamic quantities of de Sitter black holes. It is found that these effective thermodynamic quantities also satisfy Smarr-like formula. Especially, the effective temperatures are nonzero in the Nariai limit. By calculating heat capacity and Gibbs free energy, we find SdS black hole is always thermodynamically stable and RNdS black hole may undergoes phase transition at some points.

  14. Thermodynamics in Fractional Calculus

    NASA Astrophysics Data System (ADS)

    Meilanov, R. P.; Magomedov, R. A.

    2014-11-01

    A generalization of thermodynamics in the formalism of fractional-order derivatives is given. Results of the traditional thermodynamics of Carnot, Clausius, and Helmholtz are obtained in the particular case where the exponent of a fractional-order derivative is equal to unity. A one-parametric "fractal" equation of state is obtained with account of the second virial coefficient. The application of the resulting equation of state in the case of the gas argon is considered.

  15. Effective Career Exploration Programs Revisited.

    ERIC Educational Resources Information Center

    Wiggins, James D.

    1987-01-01

    Replicated findings of Wiggins and Moody (1981). Evaluated four types of high school career exploration programs: cluster (N=53), Career Maturity Inventory (N=52), Career Survey (N=57), and Self-Directed Search/Vocational Preference Inventory (N=55). Results favored latter three programs which allowed students to pursue their own interests instead…

  16. Distribution of Fullerene Nanoparticles between Water and Solid Supported Lipid Membranes: Thermodynamics and Effects of Membrane Composition on Distribution.

    PubMed

    Ha, Yeonjeong; Katz, Lynn E; Liljestrand, Howard M

    2015-12-15

    The distribution coefficient (Klipw) of fullerene between solid supported lipid membranes (SSLMs) and water was examined using different lipid membrane compositions. Klipw of fullerene was significantly higher with a cationic lipid membrane compared to that with a zwitterionic or anionic lipid membrane, potentially due to the strong interactions between negative fullerene dispersions and positive lipid head groups. The higher Klipw for fullerene distribution to ternary lipid mixture membranes was attributed to an increase in the interfacial surface area of the lipid membrane resulting from phase separation. These results imply that lipid composition can be a critical factor that affects bioconcentration of fullerene. Distribution of fullerene into zwitterionic unsaturated lipid membranes was dominated by the entropy contribution (ΔS) and the process was endothermic (ΔH > 0). This result contrasts the partitioning thermodynamics of highly and moderately hydrophobic chemicals indicating that the lipid-water distribution mechanism of fullerene may be different from that of molecular level chemicals. Potential mechanisms for the distribution of fullerene that may explain these differences include adsorption on the lipid membrane surfaces and partitioning into the center of lipid membranes (i.e., absorption).

  17. Thermodynamic aspects of cholesterol effect on properties of phospholipid monolayers: Langmuir and Langmuir-Blodgett monolayer study.

    PubMed

    Jurak, Małgorzata

    2013-04-04

    Cholesterol is an important component of lipid rafts in mammalian cell membranes. Studies of phospholipid monolayers containing cholesterol provide insight into the role of cholesterol in regulating the properties of animal cells, raft stability, and organization. In this contribution, a study of the characteristics of binary Langmuir monolayers consisting of phospholipids, 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC), 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC), 2-oleoyl-1-palmitoyl-sn-glycero-3-phosphocholine (POPC), 1,2-dipalmitoyl-sn-glycero-3-phospho-rac-(1-glycerol) (DPPG), and cholesterol (Chol), was conducted on the basis of the surface pressure-area per molecule (π-A) isotherms. Analysis of the results obtained provided information on the mean molecular area, the excess Gibbs energy of mixing, and condensation in the monolayer. The mixed monolayers were also deposited onto the mica plates and investigated by the contact angle measurements of water, formamide, and diiodomethane. The contact angles allowed calculating surface free energy of the films from the van Oss et al. approach. It was found that cholesterol determines the molecular packing and ordering of the monolayers closely connected with the kind of phospholipid. This is reflected in the values of surface free energy of the model membranes. From the thermodynamic analysis of phospholipid/cholesterol/liquid interactions, one may draw conclusions about the most favorable composition (stoichiometry) of the binary film which is especially important in view of the lipid rafts formation.

  18. First Grade Writers Revisit Their Work

    ERIC Educational Resources Information Center

    Hansen, Jane A.

    2007-01-01

    In this article, the author focuses on first grade readers and writers who revisit their work and describes what first-graders do when they revisit their writing about science and literature and review collections of their work. The first-graders discussed here are in Elaine O'Connor's classroom at Clark Elementary School in Charlottesville. In a…

  19. Effect of intramolecular Paternò-Büchi reaction on the thermodynamics and kinetics of nearly degenerate [3,3]-sigmatropic shift in fluxional polycycles.

    PubMed

    Valiulin, Roman A; Dressen, Donald G; Riggs, Jennifer R; Habte, Faven M; Kutateladze, Andrei G

    2009-05-01

    In reactions with weak dienophiles, cyclooctatetraene (COT) often yields 2:1 adducts possessing the fluxional bicyclo[5.1.0]octadiene moiety. They undergo fast, nearly degenerate Cope rearrangement with an activation barrier similar to that of the parent dihydrobullvalene. Irradiation to excite the carbonyl moiety induces an intramolecular Paterno-Buchi cyclization yielding endo-oxetanes and significantly changing the Cope-averaged NMR spectra. In this paper we examine the effect of skeletal distortion caused by intramolecular [2 + 2]-photoaddition on thermodynamics and the activation barrier of the [3,3]-sigmatropic tautomerism. Our finding is that such a distortion lifts the energetic degeneracy of the two valence tautomers, while not affecting the activation barrier.

  20. The kinetic and thermodynamic sorption and stabilization of multiwalled carbon nanotubes in natural organic matter surrogate solutions: the effect of surrogate molecular weight.

    PubMed

    Li, Tingting; Lin, Daohui; Li, Lu; Wang, Zhengyu; Wu, Fengchang

    2014-03-01

    Styrene sulfonate (SS) and polystyrene sulfonates (PSSs) were used as surrogates of natural organic matter to study the effect of molecular weight (from 206.2 to 70,000 Da) on their sorption by a multiwalled carbon nanotube (MWCNT) and an activated carbon (AC) and on their stabilization of MWCNT suspension. Results indicate that surface-diffusion through the liquid-sorbent boundary was the rate-controlling step of the kinetic sorption of both MWCNTs and AC, and surface-occupying and pore-filling mechanisms respectively dominated the thermodynamic sorption of MWCNTs and AC. Sorption rates and capacities of MWCNTs and AC in molecular concentration of SS and PSS decreased with increasing molecular weight. The PSSs but not SS facilitated the stabilization of MWCNT suspension because of the increased electrosteric repulsion. The PSSs with more monomers had greater capabilities to stabilize the MWCNT suspension, but the capabilities were comparable after being normalized by the total monomer number.

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

    SciTech Connect

    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.

  2. Asymptotic structure of electrodynamics revisited

    NASA Astrophysics Data System (ADS)

    Herdegen, Andrzej

    2017-03-01

    We point out that recently published analyses of null and timelike infinity and long-range structures in electrodynamics to large extent rediscover results present in the literature. At the same time, some of the conclusions these recent works put forward may prove controversial. In view of these facts, we find it desirable to revisit the analysis taken up more than two decades ago, starting from earlier works on null infinity by other authors.

  3. Nonequilibrium thermodynamics of pressure solution

    NASA Astrophysics Data System (ADS)

    Lehner, F. K.; Bataille, J.

    1984-01-01

    This paper is concerned with the thermodynamic theory of solution and precipitation processes in wet crustal rocks and with the mechanism of steady pressure-solution slip in ‘contact zones,’ such as grain-to-grain contacts, fracture surfaces, and permeable gouge layers, that are infiltrated by a mobile aqueous solution phase. A local dissipation jump condition at the phase boundary is fundamental to identifying the thermodynamic force driving the solution and precipitation process and is used here in setting up linear phenomenological relations to model near-equilibrium phase transformation kinetics. The local thermodynamic equilibrium of a stressed pure solid in contact with its melt or solution phase is governed by Gibbs's relation, which is rederived here, in a manner emphasizing its independence of constitutive assumptions for the solid while neglecting surface tension and diffusion in the solid. Fluid-infiltrated contact zones, such as those formed by rough surfaces, cannot generally be in thermodynamic equilibrium, especially during an ongoing process of pressure-solution slip, and the existing equilibrium formulations are incorrect in overlooking dissipative processes tending to eliminate fluctuations in superficial free energies due to stress concentrations near asperities, defects, or impurities. Steady pressure-solution slip is likely to exhibit a nonlinear dependence of slip rate on shear stress and effective normal stress, due to a dependence of the contact-zone state on the latter. Given that this dependence is negligible within some range, linear relations for pressure-solution slip can be derived for the limiting cases of diffusion-controlled and interface-reaction-controlled rates. A criterion for rate control by one of these mechanisms is set by the magnitude of the dimensionless quantity kδ/2C pD, where k is the interfacial transfer coefficient, δ is the mean diffusion path length, C p is the solubility at pressure p, and D is the mass

  4. Thermodynamics and evolution.

    PubMed

    Demetrius, L

    2000-09-07

    The science of thermodynamics is concerned with understanding the properties of inanimate matter in so far as they are determined by changes in temperature. The Second Law asserts that in irreversible processes there is a uni-directional increase in thermodynamic entropy, a measure of the degree of uncertainty in the thermal energy state of a randomly chosen particle in the aggregate. The science of evolution is concerned with understanding the properties of populations of living matter in so far as they are regulated by changes in generation time. Directionality theory, a mathematical model of the evolutionary process, establishes that in populations subject to bounded growth constraints, there is a uni-directional increase in evolutionary entropy, a measure of the degree of uncertainty in the age of the immediate ancestor of a randomly chosen newborn. This article reviews the mathematical basis of directionality theory and analyses the relation between directionality theory and statistical thermodynamics. We exploit an analytic relation between temperature, and generation time, to show that the directionality principle for evolutionary entropy is a non-equilibrium extension of the principle of a uni-directional increase of thermodynamic entropy. The analytic relation between these directionality principles is consistent with the hypothesis of the equivalence of fundamental laws as one moves up the hierarchy, from a molecular ensemble where the thermodynamic laws apply, to a population of replicating entities (molecules, cells, higher organisms), where evolutionary principles prevail.

  5. Revisiting instanton corrections to the Konishi multiplet

    NASA Astrophysics Data System (ADS)

    Alday, Luis F.; Korchemsky, Gregory P.

    2016-12-01

    We revisit the calculation of instanton effects in correlation functions in N=4 SYM involving the Konishi operator and operators of twist two. Previous studies revealed that the scaling dimensions and the OPE coefficients of these operators do not receive instanton corrections in the semiclassical approximation. We go beyond this approximation and demonstrate that, while operators belonging to the same N=4 supermultiplet ought to have the same conformal data, the evaluation of quantum instanton corrections for one operator can be mapped into a semiclassical computation for another operator in the same supermultiplet. This observation allows us to compute explicitly the leading instanton correction to the scaling dimension of operators in the Konishi supermultiplet as well as to their structure constants in the OPE of two half-BPS scalar operators. We then use these results, together with crossing symmetry, to determine instanton corrections to scaling dimensions of twist-four operators with large spin.

  6. Effect of dispersive long-range corrections to the pressure tensor: the vapour-liquid interfacial properties of the Lennard-Jones system revisited.

    PubMed

    Martínez-Ruiz, F J; Blas, F J; Mendiboure, B; Moreno-Ventas Bravo, A I

    2014-11-14

    We propose an extension of the improved version of the inhomogeneous long-range corrections of Janeček [J. Phys. Chem. B 110, 6264-6269 (2006)], presented recently by MacDowell and Blas [J. Chem. Phys. 131, 074705 (2009)] to account for the intermolecular potential energy of spherical, rigid, and flexible molecular systems, to deal with the contributions to the microscopic components of the pressure tensor due to the dispersive long-range corrections. We have performed Monte Carlo simulations in the canonical ensemble to obtain the interfacial properties of spherical Lennard-Jones molecules with different cutoff distances, r(c) = 2.5, 3, 4, and 5σ. In addition, we have also considered cutoff distances r(c) = 2.5 and 3σ in combination with the inhomogeneous long-range corrections proposed in this work. The normal and tangential microscopic components of the pressure tensor are obtained using the mechanical or virial route in combination with the recipe of Irving and Kirkwood, while the macroscopic components are calculated using the Volume Perturbation thermodynamic route proposed by de Miguel and Jackson [J. Chem. Phys. 125, 164109 (2006)]. The vapour-liquid interfacial tension is evaluated using three different procedures, the Irving-Kirkwood method, the difference between the macroscopic components of the pressure tensor, and the Test-Area methodology. In addition to the pressure tensor and the surface tension, we also obtain density profiles, coexistence densities, vapour pressure, critical temperature and density, and interfacial thickness as functions of temperature, paying particular attention to the effect of the cutoff distance and the long-range corrections on these properties. According to our results, the main effect of increasing the cutoff distance (at fixed temperature) is to sharpen the vapour-liquid interface, to decrease the vapour pressure, and to increase the width of the biphasic coexistence region. As a result, the interfacial thickness

  7. Effect of dispersive long-range corrections to the pressure tensor: The vapour-liquid interfacial properties of the Lennard-Jones system revisited

    SciTech Connect

    Martínez-Ruiz, F. J.; Blas, F. J.; Mendiboure, B.; Moreno-Ventas Bravo, A. I.

    2014-11-14

    We propose an extension of the improved version of the inhomogeneous long-range corrections of Janeček [J. Phys. Chem. B 110, 6264–6269 (2006)], presented recently by MacDowell and Blas [J. Chem. Phys. 131, 074705 (2009)] to account for the intermolecular potential energy of spherical, rigid, and flexible molecular systems, to deal with the contributions to the microscopic components of the pressure tensor due to the dispersive long-range corrections. We have performed Monte Carlo simulations in the canonical ensemble to obtain the interfacial properties of spherical Lennard-Jones molecules with different cutoff distances, r{sub c} = 2.5, 3, 4, and 5σ. In addition, we have also considered cutoff distances r{sub c} = 2.5 and 3σ in combination with the inhomogeneous long-range corrections proposed in this work. The normal and tangential microscopic components of the pressure tensor are obtained using the mechanical or virial route in combination with the recipe of Irving and Kirkwood, while the macroscopic components are calculated using the Volume Perturbation thermodynamic route proposed by de Miguel and Jackson [J. Chem. Phys. 125, 164109 (2006)]. The vapour-liquid interfacial tension is evaluated using three different procedures, the Irving-Kirkwood method, the difference between the macroscopic components of the pressure tensor, and the Test-Area methodology. In addition to the pressure tensor and the surface tension, we also obtain density profiles, coexistence densities, vapour pressure, critical temperature and density, and interfacial thickness as functions of temperature, paying particular attention to the effect of the cutoff distance and the long-range corrections on these properties. According to our results, the main effect of increasing the cutoff distance (at fixed temperature) is to sharpen the vapour-liquid interface, to decrease the vapour pressure, and to increase the width of the biphasic coexistence region. As a result, the interfacial

  8. Universalities of thermodynamic signatures in topological phases

    PubMed Central

    Kempkes, S. N.; Quelle, A.; Smith, C. Morais

    2016-01-01

    Topological insulators (superconductors) are materials that host symmetry-protected metallic edge states in an insulating (superconducting) bulk. Although they are well understood, a thermodynamic description of these materials remained elusive, firstly because the edges yield a non-extensive contribution to the thermodynamic potential, and secondly because topological field theories involve non-local order parameters, and cannot be captured by the Ginzburg-Landau formalism. Recently, this challenge has been overcome: by using Hill thermodynamics to describe the Bernevig-Hughes-Zhang model in two dimensions, it was shown that at the topological phase transition the thermodynamic potential does not scale extensively due to boundary effects. Here, we extend this approach to different topological models in various dimensions (the Kitaev chain and Su-Schrieffer-Heeger model in one dimension, the Kane-Mele model in two dimensions and the Bernevig-Hughes-Zhang model in three dimensions) at zero temperature. Surprisingly, all models exhibit the same universal behavior in the order of the topological-phase transition, depending on the dimension. Moreover, we derive the topological phase diagram at finite temperature using this thermodynamic description, and show that it displays a good agreement with the one calculated from the Uhlmann phase. Our work reveals unexpected universalities and opens the path to a thermodynamic description of systems with a non-local order parameter. PMID:27929041

  9. Universalities of thermodynamic signatures in topological phases

    NASA Astrophysics Data System (ADS)

    Kempkes, S. N.; Quelle, A.; Smith, C. Morais

    2016-12-01

    Topological insulators (superconductors) are materials that host symmetry-protected metallic edge states in an insulating (superconducting) bulk. Although they are well understood, a thermodynamic description of these materials remained elusive, firstly because the edges yield a non-extensive contribution to the thermodynamic potential, and secondly because topological field theories involve non-local order parameters, and cannot be captured by the Ginzburg-Landau formalism. Recently, this challenge has been overcome: by using Hill thermodynamics to describe the Bernevig-Hughes-Zhang model in two dimensions, it was shown that at the topological phase transition the thermodynamic potential does not scale extensively due to boundary effects. Here, we extend this approach to different topological models in various dimensions (the Kitaev chain and Su-Schrieffer-Heeger model in one dimension, the Kane-Mele model in two dimensions and the Bernevig-Hughes-Zhang model in three dimensions) at zero temperature. Surprisingly, all models exhibit the same universal behavior in the order of the topological-phase transition, depending on the dimension. Moreover, we derive the topological phase diagram at finite temperature using this thermodynamic description, and show that it displays a good agreement with the one calculated from the Uhlmann phase. Our work reveals unexpected universalities and opens the path to a thermodynamic description of systems with a non-local order parameter.

  10. Thermodynamics of Nonadditive Systems.

    PubMed

    Latella, Ivan; Pérez-Madrid, Agustín; Campa, Alessandro; Casetti, Lapo; Ruffo, Stefano

    2015-06-12

    The usual formulation of thermodynamics is based on the additivity of macroscopic systems. However, there are numerous examples of macroscopic systems that are not additive, due to the long-range character of the interaction among the constituents. We present here an approach in which nonadditive systems can be described within a purely thermodynamics formalism. The basic concept is to consider a large ensemble of replicas of the system where the standard formulation of thermodynamics can be naturally applied and the properties of a single system can be consequently inferred. After presenting the approach, we show its implementation in systems where the interaction decays as 1/r(α) in the interparticle distance r, with α smaller than the embedding dimension d, and in the Thirring model for gravitational systems.

  11. The effect of pressure on the structural, electronic, magnetic, and thermodynamic properties of the Mn2RuGe inverse Heusler alloy

    NASA Astrophysics Data System (ADS)

    Song, Ting; Sun, Xiao-Wei; Tian, Jun-Hong; Wei, Xiao-Ping; Wan, Gui-Xin; Ma, Qin

    2017-04-01

    In the frame of density functional theory, first-principles calculations based on generalized gradient approximation and quasi-harmonic Debye approximation model in which the phononic effects are taken into account have been carried out to investigate the structural, electronic, magnetic, and thermodynamic properties of full-Heusler alloy Mn2RuGe in CuHg2Ti-type structure in the pressure range of 0-50 GPa. Present calculations predict that Mn2RuGe is a ferrimagnet with an optimized lattice parameter of 5.854 Å. The calculated total magnetic moment of 2.01 μB per formula unit is very close to integer value and agree well with the Slater-Pauling rule, where the partial spin moments of Mn (A) and Mn (B) which mainly contribute to the total magnetic moment are 2.66 μB and -0.90 μB, respectively. In the study of the energy band structures and density of states, Mn2RuGe exhibits half-metallicity with an indirect gap of 0.235 eV in the spin-down channels, and the shifting of bands towards higher energies in spin-down channel under high pressure. Meanwhile, the high-pressure thermodynamic properties of Mn2RuGe, such as the pressure-volume-temperature relationship, bulk modulus, thermal expansivity, heat capacity, Debye temperature, and Grüneisen parameter are evaluated systematically in the temperature range of 0-900 K. This set of data is considered as the useful information to understand the high-pressure and high-temperature properties for the Mn2RuZ-type Heusler alloy family.

  12. Methanol conversion to light olefins over nanostructured CeAPSO-34 catalyst: Thermodynamic analysis of overall reactions and effect of template type on catalytic properties and performance

    SciTech Connect

    Aghamohammadi, Sogand; Haghighi, Mohammad; Charghand, Mojtaba

    2014-02-01

    Graphical abstract: In this research nanostructured CeAPSO-34 was synthesized to explore the effect of TEAOH and morpholine on its physiochemical properties and MTO performance. Prepared catalysts were characterized with XRD, FESEM, BET, FTIR and NH3-TPD techniques. The results indicated that the nature of the template determines the physiochemical properties of CeAPSO-34 due to different rate of crystal growth. The catalyst obtained by using morpholine showed longer life time as well as sustaining light olefins selectivity at higher values. Furthermore, a comprehensive thermodynamic analysis of overall reactions network was carried out to address the major channels of methanol to olefins conversion. - Highlights: • Introduction of Ce into SAPO-34 framework. • Comparison of CeAPSO-34 synthesized using morpholine and TEAOH. • The nature of the template determines the physiochemical properties of CeAPSO-34. • Morpholine enhances catalyst lifetime in MTO process. • Presenting a complete reaction network for MTO process. - Abstract: TEAOH and morpholine were employed in synthesis of nanostructured CeAPSO-34 molecular sieve and used in methanol to olefins conversion. Prepared samples were characterized by XRD, FESEM, EDX, BET, FTIR and NH{sub 3}-TPD techniques. XRD patterns reflected the higher crystallinity of the catalyst synthesized with morpholine. The FESEM results indicated that the nature of the template determines the morphology of nanostructured CeAPSO-34 due to different rate of crystal growth. There was a meaningful difference in the strength of both strong and weak acid sites for CeAPSO-34 catalysts synthesized with TEAOH and morpholine templates. The catalyst synthesized with morpholine showed higher desorption temperature of both weak and strong acid sites evidenced by NH{sub 3}-TPD characterization. The catalyst obtained using morpholine template had the longer lifetime and sustained desired light olefins at higher values. A comprehensive

  13. Effects of temperature on the thermodynamic and dynamical properties of glycerol-water mixtures: a computer simulation study of three different force fields.

    PubMed

    Akinkunmi, Frederick O; Jahn, David A; Giovambattista, Nicolas

    2015-05-21

    Glycerol-water solutions are relevant in technological and scientific applications, such as in the preservation of biomolecules and tissues at low temperatures. We perform molecular dynamics simulations of glycerol-water mixtures with glycerol molar fractions of χg = 0-100% at P = 0.1 MPa and T = 210-460 K. We focus on the effects of temperature and concentration on the thermodynamic (density ρ, thermal expansion coefficient αP, isobaric specific heat cP, compressibility κT) and dynamical (glycerol and water diffusion coefficients, Dg and Dw) properties of the mixtures. In particular, we test the sensitivity of computer simulation results to the glycerol force field and water model (TIP3P and TIP4P/2005) employed. All mixture models underestimate ρ at high T and tend to overestimate ρ at low T; only the mixture model based on TIP4P/2005 water exhibits a density maximum at low χg, as expected. All models overestimate αP, cP, and κT; they are able to reproduce qualitatively the T dependence of αP and κT but fail in the case of cP. In all cases, Dg and Dw follow the Vogel-Tamman-Fulcher equation and decouple at low T, with Dw/Dg increasing upon cooling. Overall, the mixture based on TIP4P/2005 water provides better thermodynamic and dynamical properties than the mixtures based on TIP3P water, even at χg = 20%.

  14. Effect of stacking interactions on the thermodynamics and kinetics of lumiflavin: a study with improved density functionals and density functional tight-binding protocol.

    PubMed

    Bresnahan, Caitlin G; Reinhardt, Clorice R; Bartholow, Thomas G; Rumpel, John P; North, Michael; Bhattacharyya, Sudeep

    2015-01-08

    The π-π stacking interaction between lumiflavin and a number of π-electron-rich molecules has been studied by density functional theory using several new-generation density functionals. Six known lumiflavin-aromatic adducts were used and the models were evaluated by comparing the geometry and energetics with experimental results. The study found that dispersion-corrected and hybrid functionals with larger (>50%) Hartree-Fock exchanges produced superior results in modeling thermodynamic characteristics of these complexes. The functional producing the best energetics for these model systems was used to study the stacking interactions of lumiflavin with biologically relevant aromatic groups. Additionally, the reduction of flavin-in the presence of both a hydride donor and a nondonor π-electronic system was also studied. Weak interactions were observed in the stacked lumiflavin complexes of benzene, phenol, and indole, mimicking phenyl alanine, tryptophan, and tyrosine side chains, respectively, of an enzyme. The stacked complex of naphthalene and flavin showed little change in flavin's redox potential indicating insignificant effect on the thermodynamics of the hydride transfer reaction. In contrast, the hydride transfer reaction with the hydride donor N-methyl nicotinamide tells a different story, as the transition state was found to be strongly impacted by the stacking interactions. A comparison of performance between the density functional theory (DFT) and the computationally less expensive dispersion-corrected self-consistent density functional tight-binding (SCC-DFTB-D) theory revealed that the latter produces consistent energetics for this hydride transfer reaction and additional DFT-computed perturbative corrections could significantly improve these results.

  15. The Aqueous Thermodynamics and Complexation Reactions of Anionic Silica Species to High Concentration: Effects on Neutralization of Leaked Tank Wastes and Migration of Radionuclides in the Subsurface

    SciTech Connect

    Felmy, Andrew R.; Choppin, Gregory; Dixon, David A.

    2002-06-01

    Highly basic tank wastes contain several important radionuclides, including {sup 90}Sr, {sup 99}Tc, and {sup 60}Co, as well as actinide elements (i.e., isotopes of U, Pu, and Am). These highly basic tank wastes are known to have leaked into the vadose zone at the Hanford Site. Upon entering the sediments in the vadose zone, the highly basic solutions dissolve large concentrations of silica from the silica and aluminosilicate minerals present in the subsurface. These dissolution reactions alter the chemical composition of the leaking solutions, transforming them from a highly basic (as high as 2M NaOH) solution into a pore solution with a very high concentration of dissolved silica and a significantly reduced pH. This moderately basic (pH 9 to 11), high-silica solution has the potential to complex radionuclides and move through the subsurface. Such strong radionuclide complexation is a currently unconsidered transport vector that has the potential to expedite radionuclide transport through the vadose zone. These strong complexation effects have the ability to significantly alter current conceptual models of contaminant migration beneath leaking tanks. In this project, we are determining the aqueous thermodynamics and speciation of dissolved silica and silica-radionuclide complexes to high silica concentration using a combination of (1) studies of chemical species structure and composition [via nuclear magnetic resonance (NMR) and, where applicable, laser-induced fluorescence spectroscopy and x-ray absorption spectroscopy] (2) molecular simulations to help identify key species structures and assist in interpreting experimental measurements (3) fundamental physical chemistry measurements, including solubility, electromotive force, and isopiestic measurements, to obtain the necessary thermodynamic data for predicting contaminant complexation and waste neutralization reactions. The radioactive elements we are studying include Sr, Co, Cs, Am(III), and U(VI).

  16. Thermodynamics of graphene

    NASA Astrophysics Data System (ADS)

    Rusanov, A. I.

    2014-12-01

    The 21st century has brought a lot of new results related to graphene. Apparently, graphene has been characterized from all points of view except surface science and, especially, surface thermodynamics. This report aims to close this gap. Since graphene is the first real two-dimensional solid, a general formulation of the thermodynamics of two-dimensional solid bodies is given. The two-dimensional chemical potential tensor coupled with stress tensor is introduced, and fundamental equations are derived for energy, free energy, grand thermodynamic potential (in the classical and hybrid forms), enthalpy, and Gibbs energy. The fundamentals of linear boundary phenomena are formulated with explaining the concept of a dividing line, the mechanical and thermodynamic line tensions, line energy and other linear properties with necessary thermodynamic equations. The one-dimensional analogs of the Gibbs adsorption equation and Shuttleworth-Herring relation are presented. The general thermodynamic relationships are illustrated with calculations based on molecular theory. To make the reader sensible of the harmony of chemical and van der Waals forces in graphene, the remake of the classical graphite theory is presented with additional variable combinations of graphene sheets. The calculation of the line energy of graphene is exhibited including contributions both from chemical bonds and van der Waals forces (expectedly, the latter are considerably smaller than the former). The problem of graphene holes originating from migrating vacancies is discussed on the basis of the Gibbs-Curie principle. An important aspect of line tension is the planar sheet/nanotube transition where line tension acts as a driving force. Using the bending stiffness of graphene, the possible radius range is estimated for achiral (zigzag and armchair) nanotubes.

  17. The thermodynamics of general and local anesthesia.

    PubMed

    Graesbøll, Kaare; Sasse-Middelhoff, Henrike; Heimburg, Thomas

    2014-05-20

    General anesthetics are known to cause depression of the freezing point of transitions in biomembranes. This is a consequence of ideal mixing of the anesthetic drugs in the membrane fluid phase and exclusion from the solid phase. Such a generic law provides physical justification of the famous Meyer-Overton rule. We show here that general anesthetics, barbiturates, and local anesthetics all display the same effect on melting transitions. Their effect is reversed by hydrostatic pressure. Thus, the thermodynamic behavior of local anesthetics is very similar to that of general anesthetics. We present a detailed thermodynamic analysis of heat capacity profiles of membranes in the presence of anesthetics. Using this analysis, we are able to describe experimentally observed calorimetric profiles and predict the anesthetic features of arbitrary molecules. In addition, we discuss the thermodynamic origin of the cutoff effect of long-chain alcohols and the additivity of the effect of general and local anesthetics.

  18. The Thermodynamics of General and Local Anesthesia

    NASA Astrophysics Data System (ADS)

    Græsbøll, Kaare; Sasse-Middelhoff, Henrike; Heimburg, Thomas

    2014-05-01

    General anesthetics are known to cause depression of the freezing point of transitions in biomembranes. This is a consequence of ideal mixing of the anesthetic drugs in the membrane fluid phase and exclusion from the solid phase. Such a generic law provides physical justification of the famous Meyer-Overton rule. We show here that general anesthetics, barbiturates and local anesthetics all display the same effect on melting transitions. Their effect is reversed by hydrostatic pressure. Thus, the thermodynamic behavior of local anesthetics is very similar to that of general anesthetics. We present a detailed thermodynamic analysis of heat capacity profiles of membranes in the presence of anesthetics. This analysis is able to describe experimentally observed calorimetric profiles and permits prediction of the anesthetic features of arbitrary molecules. In addition, we discuss the thermodynamic origin of the cutoff-effect of long-chain alcohols and the additivity of the effect of general and local anesthetics.

  19. Inflight thermodynamic properties

    NASA Technical Reports Server (NTRS)

    Brown, S. C.; Daniels, G. E.; Johnson, D. L.; Smith, O. E.

    1973-01-01

    The inflight thermodynamic parameters (temperature, pressure, and density) of the atmosphere are presented. Mean and extreme values of the thermodynamic parameters given here can be used in application of many aerospace problems, such as: (1) research and planning and engineering design of remote earth sensing systems; (2) vehicle design and development; and (3) vehicle trajectory analysis, dealing with vehicle thrust, dynamic pressure, aerodynamic drag, aerodynamic heating, vibration, structural and guidance limitations, and reentry analysis. Atmospheric density plays a very important role in most of the above problems. A subsection on reentry is presented, giving atmospheric models to be used for reentry heating, trajectory, etc., analysis.

  20. Mechanics, Waves and Thermodynamics

    NASA Astrophysics Data System (ADS)

    Ranjan Jain, Sudhir

    2016-05-01

    Figures; Preface; Acknowledgement; 1. Energy, mass, momentum; 2. Kinematics, Newton's laws of motion; 3. Circular motion; 4. The principle of least action; 5. Work and energy; 6. Mechanics of a system of particles; 7. Friction; 8. Impulse and collisions; 9. Central forces; 10. Dimensional analysis; 11. Oscillations; 12. Waves; 13. Sound of music; 14. Fluid mechanics; 15. Water waves; 16. The kinetic theory of gases; 17. Concepts and laws of thermodynamics; 18. Some applications of thermodynamics; 19. Basic ideas of statistical mechanics; Bibliography; Index.

  1. Thermodynamics and evolutionary genetics

    NASA Astrophysics Data System (ADS)

    Müller, Ingo

    2010-03-01

    Thermodynamics and evolutionary genetics have something in common. Thus, the randomness of mutation of cells may be likened to the random thermal fluctuations in a gas. And the probabilistic nature of entropy in statistical thermodynamics can be carried over to a population of haploid and diploid cells without any conceptual change. The energetic potential wells in which the atoms of a liquid are caught correspond to selective advantages for some phenotype over others. Thus, the eventual stable state in a population comes about as a compromise in the universal competition between entropy and energy.

  2. Beyond Equilibrium Thermodynamics

    NASA Astrophysics Data System (ADS)

    Öttinger, Hans Christian

    2005-01-01

    Beyond Equilibrium Thermodynamics fills a niche in the market by providing a comprehensive introduction to a new, emerging topic in the field. The importance of non-equilibrium thermodynamics is addressed in order to fully understand how a system works, whether it is in a biological system like the brain or a system that develops plastic. In order to fully grasp the subject, the book clearly explains the physical concepts and mathematics involved, as well as presenting problems and solutions; over 200 exercises and answers are included. Engineers, scientists, and applied mathematicians can all use the book to address their problems in modelling, calculating, and understanding dynamic responses of materials.

  3. THERMODYNAMIC MODELING AND FIRST-PRINCIPLES CALCULATIONS

    SciTech Connect

    Turchi, P; Abrikosov, I; Burton, B; Fries, S; Grimvall, G; Kaufman, L; Korzhavyi, P; Manga, R; Ohno, M; Pisch, A; Scott, A; Zhang, W

    2005-12-15

    The increased application of quantum mechanical-based methodologies to the study of alloy stability has required a re-assessment of the field. The focus is mainly on inorganic materials in the solid state. In a first part, after a brief overview of the so-called ab initio methods with their approximations, constraints, and limitations, recommendations are made for a good usage of first-principles codes with a set of qualifiers. Examples are given to illustrate the power and the limitations of ab initio codes. However, despite the ''success'' of these methodologies, thermodynamics of complex multi-component alloys, as used in engineering applications, requires a more versatile approach presently afforded within CALPHAD. Hence, in a second part, the links that presently exist between ab initio methodologies, experiments, and CALPHAD approach are examined with illustrations. Finally, the issues of dynamical instability and of the role of lattice vibrations that still constitute the subject of ample discussions within the CALPHAD community are revisited in the light of the current knowledge with a set of recommendations.

  4. Thermodynamic studies on the solvent effects in chromatography on molecularly imprinted polymers. 1. Nature of the organic modifier.

    PubMed

    Kim, Hyunjung; Guiochon, Georges

    2005-03-15

    Molecularly imprinted polymers (MIPs) are used as highly enantioselective stationary phases in liquid chromatography. To optimize the binding performance of MIPs, different types of polar modifiers are frequently used. Previous studies have shown that the hydrogen-bonding donor parameter (HBD) of the modifier has a large influence on the binding performance of MIPs in chiral separations. This possibility is addressed in a detailed thermodynamic study of a Fmoc-L-tryptophan (Fmoc-L-Trp) imprinted polymer, eluted with four different polar modifiers, i.e., THF, propan-2-ol, methanol, and acetic acid, which have different HBDs (0.00, 0.33, 0.43, and 0.61, respectively). Adsorption isotherm data for each enantiomer in each of these organic modifiers were acquired by frontal analysis over a 20 000 dynamic concentration range. Nonlinear regression of the isotherm data, along with independent calculation of the affinity energy distributions, identified four different types of binding sites coexisting for the enantiomers on the MIP. The exception was acetic acid, which has the highest HBD. In this case, three types of binding sites only coexist on the MIP. The isotherm parameters obtained from these data show the following: (1) The association energies of the two enantiomers with a given type of sites have a similar magnitude; however, the density of the sites is higher for the template than for its antipode. (2) The nature of the organic modifier has a larger influence on the density of high-energy sites than on the association constant of these sites. (3) The molecular size of the organic modifier has a larger influence on the site density (especially for Fmoc-D-Trp) than does HBD. (4) Using an organic modifier with a higher HBD reduces the enantioselectivity on each site. (5) High-energy sites are more enantioselective than low-energy ones. (6) Using an organic modifier with a high HBD causes a larger reduction in the density of high-energy sites approached by the

  5. Effect of side by side interactions on the thermodynamic properties of adsorbed CO molecules on the Ni(111) surface: a cluster model study

    NASA Astrophysics Data System (ADS)

    Shamkhali, Amir N.; Parsafar, Gholamabbas

    2010-05-01

    The effect of electrostatic interactions on vibrational frequencies and thermodynamic properties of CO adsorbate on the Ni(111) surface is calculated by taking the first and second nearest-neighbour interactions into account. In order to obtain reasonable results, the cluster model of various surface adsorption sites with CO adsorbate is partially optimized, using Density Functional Theory and also the MP2 method for the hcp site. Comparison between DFT and MP2 results shows that DFT results are more reliable for this system. The stretching and bending frequencies of CO adsorbate are calculated using both Partial Hessian Analysis and Cluster-Adsorbate Coupling methods. Stretching and bending frequencies are both shifted by the side by side interactions. The coupling of surface phonons and adsorbate vibrations reduces the side effects. The largest side effects on the vibrational internal energy, isochoric heat capacity, entropy and total Helmholtz free energy of adsorbed CO molecule calculated using the CAC method are found for 0.5 ML coverage. The results of the CAC method are better, but the PHA method can be used as a simple upper bound estimation. The adsorptive phase acts as an intelligent material in such a way that it changes its configuration in order to reduce the side effects.

  6. Thermodynamic stability and Watson-Crick base pairing in the seed duplex are major determinants of the efficiency of the siRNA-based off-target effect.

    PubMed

    Ui-Tei, Kumiko; Naito, Yuki; Nishi, Kenji; Juni, Aya; Saigo, Kaoru

    2008-12-01

    Short interfering RNA (siRNA) may down-regulate many unintended genes whose transcripts possess complementarity to the siRNA seed region, which contains 7 nt. The capability of siRNA to induce this off-target effect was highly correlated with the calculated melting temperature or standard free-energy change for formation of protein-free seed duplex, indicating that thermodynamic stability of seed duplex formed between the seed and target is one of the major factor in determining the degree of off-target effects. Furthermore, unlike intended gene silencing (RNA interference), off-target effect was completely abolished by introduction of a G:U pair into the seed duplex, and this loss in activity was completely recovered by a second mutation regenerating Watson-Crick pairing, indicating that seed duplex Watson-Crick pairing is also essential for off-target gene silencing. The off-target effect was more sensitive to siRNA concentration compared to intended gene silencing, which requires a near perfect sequence match between the siRNA guide strand and target mRNA.

  7. The frictionless damping of a piston in thermodynamics

    NASA Astrophysics Data System (ADS)

    Bringuier, E.

    2015-09-01

    The paper revisits Rüchardt’s experiment and the two-chamber variant of Clark and Katz, where the oscillating motion of a freely sliding piston involves the adiabatic exponent of the gas enclosed in a thermally isolated chamber. While the common theoretical account of the experiment correctly predicts the frequency of the oscillation, the damping is usually ascribed to a linear frictional force of an undetermined mechanical nature. In this paper, we argue that the irreversibility of the damped motion calls for a thermodynamical treatment involving dissipation (entropy production). The theory of Rüchardt’s experiment is reworked at the undergraduate level by allowing entropy to change owing to heat transfer into or out of the chamber. It is calculated that a linear heat transfer can explain the observed damping without assuming any mechanical friction. The calculation is quantitatively supported by an experiment. It is also calculated that the mechanical and thermal equilibrations occur at the same rate. Besides possibly improving Rüchardt and Clark-and-Katz apparatuses by shedding light on the damping, the paper helps to better grasp thermodynamics, and how to use entropy, by constrasting the mechanical and thermodynamical reasonings on the example of the damped motion of a piston.

  8. Black Hole Thermodynamics in an Undergraduate Thermodynamics Course.

    ERIC Educational Resources Information Center

    Parker, Barry R.; McLeod, Robert J.

    1980-01-01

    An analogy, which has been drawn between black hole physics and thermodynamics, is mathematically broadened in this article. Equations similar to the standard partial differential relations of thermodynamics are found for black holes. The results can be used to supplement an undergraduate thermodynamics course. (Author/SK)

  9. Thermodynamics of Dilute Solutions.

    ERIC Educational Resources Information Center

    Jancso, Gabor; Fenby, David V.

    1983-01-01

    Discusses principles and definitions related to the thermodynamics of dilute solutions. Topics considered include dilute solution, Gibbs-Duhem equation, reference systems (pure gases and gaseous mixtures, liquid mixtures, dilute solutions), real dilute solutions (focusing on solute and solvent), terminology, standard states, and reference systems.…

  10. Thermodynamically Correct Bioavailability Estimations

    DTIC Science & Technology

    1992-04-30

    6448 I 1. SWPPUMENTA* NOTIS lIa. OISTUAMJTiOAVAILAIILTY STATIMENT 121 OT REbT ostwosCo z I Approved for public release; distribution unlimited... research is to develop thermodynamically correct bioavailability estimations using chromatographic stationary phases as a model of the "interphase

  11. Program Computes Thermodynamic Functions

    NASA Technical Reports Server (NTRS)

    Mcbride, Bonnie J.; Gordon, Sanford

    1994-01-01

    PAC91 is latest in PAC (Properties and Coefficients) series. Two principal features are to provide means of (1) generating theoretical thermodynamic functions from molecular constants and (2) least-squares fitting of these functions to empirical equations. PAC91 written in FORTRAN 77 to be machine-independent.

  12. Thermodynamics of liquid metal

    SciTech Connect

    Kushnirenko, A.N.

    1988-01-01

    The thermodynamics of a liquid metal based on quantum-mechanical models of the crystal, electronic, and nuclear structures of the metal are derived in this paper. The models are based on such formulations as the Bohr radius, the Boltzmann constant, the Planck Law, the Fermi surface, and the Pauli principle.

  13. Thermodynamics of Resource Recycling.

    ERIC Educational Resources Information Center

    Hauserman, W. B.

    1988-01-01

    Evaluates the overall economic efficiency of a closed resource cycle. Uses elementary thermodynamic definitions of overall thermal efficiency for determining an economically quantifiable basis. Selects aluminum for investigation and includes a value-entropy diagram for a closed aluminum cycle. (MVL)

  14. Single molecules: Thermodynamic limits

    NASA Astrophysics Data System (ADS)

    Liphardt, Jan

    2012-09-01

    Technologies aimed at single-molecule resolution of non-equilibrium systems increasingly require sophisticated new ways of thinking about thermodynamics. An elegant extension to standard fluctuation theory grants access to the kinetic intermediate states of these systems -- as DNA-pulling experiments now demonstrate.

  15. On Teaching Thermodynamics

    ERIC Educational Resources Information Center

    Debbasch, F.

    2011-01-01

    The logical structure of classical thermodynamics is presented in a modern, geometrical manner. The first and second law receive clear, operatively oriented statements and the Gibbs free energy extremum principle is fully discussed. Applications relevant to chemistry, such as phase transitions, dilute solutions theory and, in particular, the law…

  16. Available Energy via Nonequilibrium Thermodynamics.

    ERIC Educational Resources Information Center

    Woollett, E. L.

    1979-01-01

    Presents basic relations involving the concept of available energy that are derived from the local equations of nonequilibrium thermodynamics. The equations and applications of the local thermodynamic equilibrium LTD model are also presented. (HM)

  17. Fluctuating Thermodynamics for Biological Processes

    NASA Astrophysics Data System (ADS)

    Ham, Sihyun

    Because biomolecular processes are largely under thermodynamic control, dynamic extension of thermodynamics is necessary to uncover the mechanisms and driving factors of fluctuating processes. The fluctuating thermodynamics technology presented in this talk offers a practical means for the thermodynamic characterization of conformational dynamics in biomolecules. The use of fluctuating thermodynamics has the potential to provide a comprehensive picture of fluctuating phenomena in diverse biological processes. Through the application of fluctuating thermodynamics, we provide a thermodynamic perspective on the misfolding and aggregation of the various proteins associated with human diseases. In this talk, I will present the detailed concepts and applications of the fluctuating thermodynamics technology for elucidating biological processes. This work was supported by Samsung Science and Technology Foundation under Project Number SSTF-BA1401-13.

  18. CFD analysis of thermodynamic cycles in a pulse tube refrigerator

    NASA Astrophysics Data System (ADS)

    Chen, Ling; Zhang, Yu; Luo, Ercang; Li, Teng; Wei, Xiaolin

    2010-11-01

    The objectives of this paper are to study the thermodynamic cycles in an inertance tube pulse tube refrigerator (ITPTR) by means of CFD method. The simulation results show that gas parcels working in different parts of ITPTR undergo different thermodynamic cycles. The net effects of those thermodynamic cycles are pumping heat from the low temperature part to the high temperature part of the system. The simulation results also show that under different frequencies of piston movement, the gas parcels working in the same part of the system will undergo the same type of thermodynamic cycles. The simulated thermal cycles are compared with those thermodynamic analysis results from a reference. Comparisons show that both CFD simulations and theoretical analysis predict the same type of thermal cycles at the same location. However, only CFD simulation can give the quantitative results, while the thermodynamic analysis is still remaining in quality.

  19. Inconsistencies in steady state thermodynamics

    NASA Astrophysics Data System (ADS)

    Dickman, Ronald; Motai, Ricardo

    2014-03-01

    We address the issue of extending thermodynamics to nonequilibrium steady states. Using driven stochastic lattice gases, we ask whether consistent definitions of an effective chemical potential μ, and an effective temperature Te, are possible. These quantities are determined via zero-flux conditions of particles and energy between the driven system and a reservoir. For the models considered here, the fluxes are given in terms of certain stationary average densities, eliminating the need to perturb the system by actually exchanging particles; μ and Te are thereby obtained via open-circuit measurements, using a virtual reservoir. In the lattice gas with nearest-neighbor exclusion, temperature is not relevant, and we find that the effective chemical potential, a function of density and drive strength, satisfies the zeroth law, and correctly predicts the densities of coexisting systems. In the Katz-Lebowitz-Spohn driven lattice gas, both μ and Te need to be defined. We show analytically that the zeroth law is violated, and determine the size of the violations numerically. Our results highlight a fundamental inconsistency in the extension of thermodynamics to nonequilibrium steady states. Research supported by CNPq, Brazil.

  20. Lithium in the Pleiades Revisited

    NASA Astrophysics Data System (ADS)

    King, J. R.; Hobbs, L. M.; Schuler, S. C.; Pinsonneault, M. H.

    2003-12-01

    New Li abundances have been derived for some 15-20 Pleiades dwarfs using new high-resolution and high S/N spectroscopy from HET/HRS. Previous studies suggested that our objects, all modest (projected) rotators, evinced considerable scatter in their Li abundances. We revisit the question of this scatter and its origin. This work has been supported by NSF grants AST 00-86576 and 02-39518, a South Carolina Space Grant Scholarship award, a generous donation from the Curry Foundation of Seneca, SC, and the NOAO Public Access Program.