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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. 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…

  9. 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.

  10. Comment on the Article ``Relativistic Non-Equilibrium Thermodynamics Revisited''

    NASA Astrophysics Data System (ADS)

    Muschik, Wolfgang; von Borzeszkowski, Horst-Heino

    2007-05-01

    There are two problematic items in García-Colín and Sandoval-Villalbazo's approach to “relativistic non-equilibrium thermodynamics” (L.S. García- Colín and A. Sandoval-Villalbazo, J. Non-Equilib. Thermodyn. 31, 2006, pp. 11-22). The paper does not follow the fundamentals of relativity theory; according to them, the energy-momentum tensor (EMT) has to include all energies of the considered system. Secondly, strange thermodynamic consequences result by using the presuppositions made by the authors. The paper is critically discussed and some shortcomings are elucidated.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. The sentence superiority effect revisited.

    PubMed

    Snell, Joshua; Grainger, Jonathan

    2017-11-01

    A sentence superiority effect was investigated using post-cued word-in-sequence identification with the rapid parallel visual presentation (RPVP) of four horizontally aligned words. The four words were presented for 200ms followed by a post-mask and cue for partial report. They could form a grammatically correct sentence or were formed of the same words in a scrambled agrammatical sequence. Word identification was higher in the syntactically correct sequences, and crucially, this sentence superiority effect did not vary as a function of the target's position in the sequence. Cloze probability measures for words at the final, arguably most predictable position, revealed overall low values that did not interact with the effects of sentence context, suggesting that these effects were not driven by word predictability. The results point to a level of parallel processing across multiple words that enables rapid extraction of their syntactic categories. These generate a sentence-level representation that constrains the recognition process for individual words, thus facilitating parallel word processing when the sequence is grammatically sound. Copyright © 2017 Elsevier B.V. All rights reserved.

  18. 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.

  19. 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

  20. 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…

  1. 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…

  2. 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

  3. 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.

  4. 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.

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

    PubMed

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

    2016-11-14

    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.

  6. 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

  7. 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,…

  8. 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,…

  9. 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.

  10. 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.

  11. The Ti-Mn system revisited: experimental investigation and thermodynamic modelling.

    PubMed

    Khan, A U; Brož, P; Premović, M; Pavlů, J; Vřeštál, J; Yan, X; Maccio, D; Saccone, A; Giester, G; Rogl, P

    2016-08-17

    As the Ti-Mn phase diagram is part of numerous ternary and higher order systems of technological importance, the present paper defines phase relations which have been experimentally established throughout this work from 800 °C to the melting range based on Differential Thermal Analyses (DTA), X-ray powder diffraction, metallography and Electron Probe Micro Analysis (EPMA) techniques on ∼50 alloys, which were prepared by arc melting or high frequency melting under high purity argon starting from freshly cleaned metal ingots. Novel compounds were identified and reaction isotherms were redefined accordingly. In the Ti-rich region a novel compound TiMn was detected, sandwiched between the known phases: TiMn1-x (∼45 at% Mn) and TiMn1+x (∼55 at% Mn). In the Mn-rich region the hitherto unknown crystal structure of TiMn∼3 was solved from X-ray single crystal diffraction data and found to be of a unique structure type Ti6(Ti1-xMnx)6Mn25 (x = 0.462; space group Pbam (#55); a = 0.79081(3) nm, b = 2.58557(9) nm, c = 0.47931(2) nm), which consists of two consecutive layers of the hexagonal MgZn2-type Laves phase (TiMn2) and a combined layer of alternate structure blocks of MgZn2 type and Zr4Al3 type. Whereas TiMn can be considered as a line compound (solubility range <∼1 at%), the homogeneity regions of the Ti-Mn compounds are significant (determined by EPMA): TiMn1-x (44.0 to 46.6 at% Mn), TiMn1+x (54.6 to 56.3 at% Mn), Ti1+xMn2-x (MgZn2-type, 59 to 69 at% Mn at 1000 °C: -0.08 < x < 0.23), TiMn∼3 (unique type; 74 to 76.5 at% Mn) and TiMn∼4 (R-phase: Ti8(TixMn1-x)6Mn39, 80 to 84 at% Ti). Supported by ab initio calculations of the ground state energy for the Laves phase, the new experimental results enabled thermodynamic modelling of the entire Ti-Mn phase diagram providing a complete and novel set of thermodynamic data thus providing a sound basis for future thermodynamic predictions of higher order Ti-Mn-X-Y systems.

  12. 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

  13. 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

  14. 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.

  15. 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.

  16. 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.

  17. 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

  18. 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.

  19. The Thermodynamic Origin of Hofmeister Ion Effects

    PubMed Central

    Pegram, Laurel M.; Record, M. Thomas

    2009-01-01

    Quantitative interpretation and prediction of Hofmeister ion effects on protein processes, including folding and crystallization, have been elusive goals of a century of research. Here, a quantitative thermodynamic analysis, developed to treat noncoulombic interactions of solutes with biopolymer surface and recently extended to analyze the effects of Hofmeister salts on the surface tension of water, is applied to literature solubility data for small hydrocarbons and model peptides. This analysis allows us to obtain a minimum estimate of the hydration b1 (H2O Å−2) of hydrocarbon surface and partition coefficients Kp characterizing the distribution of salts and salt ions between this hydration water and bulk water. Assuming that Na+ and SO42− ions of Na2SO4 (the salt giving the largest reduction in hydrocarbon solubility as well as the largest increase in surface tension) are fully excluded from the hydration water at the hydrocarbon surface, we obtain the same b1 as for air-water surface (∼0.18 H2O Å−2). Rank orders of cation and anion partition coefficients for nonpolar surface follow the Hofmeister series for protein processes, but are strongly offset for cations in the direction of exclusion (preferential hydration). Assuming a coarse-grained decomposition of water accessible surface area (ASA) into nonpolar, polar amide, and other polar ASA and the same hydration b1 to interpret peptide solubility increments, we determine salt partition coefficients for amide surface. These partition coefficients are separated into single-ion contributions based on the observation that both Cl− and Na+ (also K+) occupy neutral positions in the middle of the anion and cation Hofmeister series for protein processes. Independent of this assignment, we find that all cations investigated are strongly accumulated at amide surface while most anions are excluded. Ion effects are independent and additive, allowing successful prediction of Hofmeister salt effects on micelle

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. Thermodynamical effects and high resolution methods for compressible fluid flows

    NASA Astrophysics Data System (ADS)

    Li, Jiequan; Wang, Yue

    2017-08-01

    One of the fundamental differences of compressible fluid flows from incompressible fluid flows is the involvement of thermodynamics. This difference should be manifested in the design of numerical schemes. Unfortunately, the role of entropy, expressing irreversibility, is often neglected even though the entropy inequality, as a conceptual derivative, is verified for some first order schemes. In this paper, we refine the GRP solver to illustrate how the thermodynamical variation is integrated into the design of high resolution methods for compressible fluid flows and demonstrate numerically the importance of thermodynamic effects in the resolution of strong waves. As a by-product, we show that the GRP solver works for generic equations of state, and is independent of technical arguments.

  8. 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.

  9. Resonance effect in the allyl cation and anion: a revisit.

    PubMed

    Mo, Yirong

    2004-08-20

    The interest over the magnitude of the conjugation effect in the allyl cation (1) and anion (2) has been revived recently by Barbour and Karty (J. Org. Chem. 2004, 69, 648-654), who derived the resonance energies of 20-22 and 17-18 kcal/mol for 1 and 2, respectively, using an empirical extrapolation approximation. This paper revisits the case by explicitly calculating the Pauling-Wheland resonance energy, which measures the stabilization from the most stable resonance structure to the delocalized energy-minimum state of a conjugated system, using our newly developed block-localized wave function (BLW) method. This BLW method has the geometrical optimization capability. The computations result in adiabatic resonance energies of 37 kcal/mol for 1 and 38 kcal/mol for 2. The significant disagreement between these values and Barbour and Karty's results originates from the neglect of structural and electronic variations in their derivation which are energy costing. Copyright 2004 American Chemical Society

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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

  17. Effective mass of quasiparticles from thermodynamics

    NASA Astrophysics Data System (ADS)

    Eich, F. G.; Holzmann, Markus; Vignale, G.

    2017-07-01

    We discuss the potential advantages of calculating the effective mass of quasiparticles in the interacting electron liquid from the low-temperature free energy vis-a-vis the conventional approach, in which the effective mass is obtained from approximate calculations of the self-energy, or from a quantum Monte Carlo evaluation of the energy of a variational "quasiparticle wave function". While raw quantum Monte Carlo data are presently too sparse to allow for an accurate determination of the effective mass, the values estimated by this method are numerically close to the ones obtained in previous calculations using diagrammatic many-body theory. In contrast to this, a recently published parametrization of quantum Monte Carlo data for the free energy of the homogeneous electron liquid yields effective masses that considerably deviate from previous calculations and even change sign for low densities, reflecting an unphysical negative entropy. We suggest that this anomaly is related to the treatment of the exchange energy at finite temperature.

  18. 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).

  19. 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.

  20. 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.

  1. The Peter Effect Revisited: Reading Habits and Attitudes of College Students

    ERIC Educational Resources Information Center

    Applegate, Anthony J.; Applegate, Mary DeKonty; Mercantini, Martha A.; McGeehan, Catherine M.; Cobb, Jeanne B.; DeBoy, Joanne R.; Modla, Virginia B.; Lewinski, Kimberly E.

    2014-01-01

    Certainly a primary goal of literacy education is the creation of avid, enthusiastic, and highly motivated readers. However, in this article revisiting the Peter Effect (Applegate & Applegate, 2004), researchers surveyed more than 1,000 college sophomores and found strikingly low levels of enthusiasm for reading. Only 46.6% of surveyed…

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. Local thermodynamic mapping for effective liquid density-functional theory

    NASA Technical Reports Server (NTRS)

    Kyrlidis, Agathagelos; Brown, Robert A.

    1992-01-01

    The structural-mapping approximation introduced by Lutsko and Baus (1990) in the generalized effective-liquid approximation is extended to include a local thermodynamic mapping based on a spatially dependent effective density for approximating the solid phase in terms of the uniform liquid. This latter approximation, called the local generalized effective-liquid approximation (LGELA) yields excellent predictions for the free energy of hard-sphere solids and for the conditions of coexistence of a hard-sphere fcc solid with a liquid. Moreover, the predicted free energy remains single valued for calculations with more loosely packed crystalline structures, such as the diamond lattice. The spatial dependence of the weighted density makes the LGELA useful in the study of inhomogeneous solids.

  9. 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.

  10. 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 .

  11. Thermodynamic instabilities and statistical effects in protoneutron stars

    NASA Astrophysics Data System (ADS)

    Gervino, G.; Lavagno, A.; Pigato, D.

    2017-08-01

    We investigate the physical properties of the protoneutron stars in the framework of a relativistic mean-field model and we study the finite-temperature equation of state in β-stable matter at fixed entropy per baryon, in the presence of hyperons, Δ-isobar resonances and trapped neutrinos. In this context, we study the possible presence of thermodynamic instabilities and a phase transition from nucleonic matter to resonance-dominated Δ-matter can take place. Such a phase transition is characterized by both mechanical instability (fluctuations on the baryon density) and by chemical-diffusive instability (fluctuations on the isospin concentration) in asymmetric nuclear matter. We show that such statistical effects could play a crucial role in the structure and in the evolution of the protoneutron stars.

  12. Nonequilibrium thermodynamics of the Markovian Mpemba effect and its inverse.

    PubMed

    Lu, Zhiyue; Raz, Oren

    2017-05-16

    Under certain conditions, it takes a shorter time to cool a hot system than to cool the same system initiated at a lower temperature. This phenomenon-the "Mpemba effect"-was first observed in water and has recently been reported in other systems. Whereas several detail-dependent explanations were suggested for some of these observations, no common underlying mechanism is known. Using the theoretical framework of nonequilibrium thermodynamics, we present a widely applicable mechanism for a similar effect, the Markovian Mpemba effect, derive a sufficient condition for its appearance, and demonstrate it explicitly in three paradigmatic systems: the Ising model, diffusion dynamics, and a three-state system. In addition, we predict an inverse Markovian Mpemba effect in heating: Under proper conditions, a cold system can heat up faster than the same system initiated at a higher temperature. We numerically demonstrate that this inverse effect is expected in a 1D antiferromagnet nearest-neighbors interacting Ising chain in the presence of an external magnetic field. Our results shed light on the mechanism behind anomalous heating and cooling and suggest that it should be possible to observe these in a variety of systems.

  13. 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.

  14. Non-equilibrium modeling of the PMSE Overshoot Effect revisited: A comprehensive study

    NASA Astrophysics Data System (ADS)

    Biebricher, Alexander; Havnes, Ove

    2012-06-01

    Numerical investigations of the Polar Mesosphere Summer Echoes (PMSE) Overshoot Effect have to date been undertaken under the premise of plasma neutrality and current equilibrium at any time. We find it necessary to revisit the calculations without these restrictions, since electrons and ions are attached to and absorbed by mesospheric dust particles at vastly different rates under PMSE conditions. We find that differences to earlier modeling might be so significant as to warrant further investigation. Furthermore, we conduct comprehensive studies of the PMSE Overshoot Effect and put the results in the context of experimental realities.

  15. 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

  16. Configurational thermodynamics of alloys from first principles: effective cluster interactions

    NASA Astrophysics Data System (ADS)

    Ruban, A. V.; Abrikosov, I. A.

    2008-04-01

    Phase equilibria in alloys to a great extent are governed by the ordering behavior of alloy species. One of the important goals of alloy theory is therefore to be able to simulate these kinds of phenomena on the basis of first principles. Unfortunately, it is impossible, even with present day total energy software, to calculate entirely from first principles the changes in the internal energy caused by changes of the atomic configurations in systems with several thousand atoms at the rate required by statistical thermodynamics simulations. The time-honored solution to this problem that we shall review in this paper is to obtain the configurational energy needed in the simulations from an Ising-type Hamiltonian with so-called effective cluster interactions associated with specific changes in the local atomic configuration. Finding accurate and reliable effective cluster interactions, which take into consideration all relevant thermal excitations, on the basis of first-principles methods is a formidable task. However, it pays off by opening new exciting perspectives and possibilities for materials science as well as for physics itself. In this paper we outline the basic principles and methods for calculating effective cluster interactions in metallic alloys. Special attention is paid to the source of errors in different computational schemes. We briefly review first-principles methods concentrating on approximations used in density functional theory calculations, Green's function method and methods for random alloys based on the coherent potential approximation. We formulate criteria for the validity of the supercell approach in the calculations of properties of random alloys. The generalized perturbation method, which is an effective and accurate tool for obtaining cluster interactions, is described in more detail. Concentrating mostly on the methodological side we give only a few examples of applications to the real systems. In particular, we show that the ground

  17. 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.

  18. 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

  19. 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)

  20. 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.

  1. 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

  2. The Revolution Revisited: Effective Schools and Systemic Reform.

    ERIC Educational Resources Information Center

    Taylor, Barbara O.; Bullard, Pamela

    A basic tenet of the effective-schools movement is that all children can master the basic skills needed to be successful in school. Today, the twin notions of equity and excellence strongly drive the school-reform movement. This book examines the effective-schools movement as a school-reform philosophy and renewal process for the present and…

  3. 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…

  4. 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…

  5. 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…

  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. Habitat destruction and the extinction debt revisited: the Allee effect.

    PubMed

    Chen, Ling-ling; Hui, Cang; Lin, Z S

    2009-09-01

    Habitat destruction, often caused by anthropogenic disturbance, can lead to the extinction of species at an unprecedented rate. It is important, therefore, to consider habitat destruction when assessing population viability. Another factor often ignored in population viability analysis, is the Allee effect that adds to the risk of populations already on the verge of extinction. Understanding the Allee effect on species dynamics and response to habitat destruction has intrinsic value in conservation prioritization. Here, the Allee effect was considered in a multi-species hierarchical competition model. Results showed that species persistence declines dramatically due to the Allee effect, and certain species become more susceptible to habitat destruction than others. Two extinction orders emerged under habitat destruction: either the best competitor becomes extinct first or the best colonizer first. The extinction debt and order, as well as the time lag between habitat destruction and species extinction, were found to be determined by species abundance and the intensity of the Allee effect.

  8. 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

  9. 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

  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. 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.

  13. Preference or fat? Revisiting opioid effects on food intake

    PubMed Central

    Taha, Sharif A.

    2010-01-01

    It is well established that opioid signaling in the central nervous system constitutes a powerful stimulus for food intake. The role of opioids in determining food preference, however, is less well defined. Opioids have been proposed to promote intake of preferred foods, or, alternatively, to preferentially increase consumption of fat. In the present manuscript, I comprehensively review results from previous studies investigating this issue. Data from these studies suggests a mechanism for opioid action that may reconcile the previously proposed hypotheses: opioid effects on food intake do appear to be largely specific for fat consumption, but individual animals’ sensitivity to this effect may be dependent on baseline food preferences. In addition, I highlight the possibility that the selectivity of endogenous opioid effects may importantly differ from that of exogenous agonists in the degree to which baseline preferences, rather than macronutrient intake, are altered. PMID:20211638

  14. 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.

  15. 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…

  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. Terminology Revisited: Effective Communications for the Agricultural Community

    USDA-ARS?s Scientific Manuscript database

    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...

  18. 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.

  19. 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…

  20. 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…

  1. Nanoscale elastic modulus mapping revisited: The concept of effective mass

    NASA Astrophysics Data System (ADS)

    Zlotnikov, I.; Fratzl, P.; Zolotoyabko, E.

    2014-09-01

    We introduce the effective mass of the nanoindenter tip/sample assembly into the nanoscale dynamic modulus mapping technique that allows us to extract the correct storage modulus from the measured contact stiffness. We show that the developed approach successfully works for both stiff ceramics, such as fused quartz, and much compliant polymer materials, such as polycarbonate (PC) and poly(methyl methacrylate) (PMMA).

  2. 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…

  3. 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…

  4. 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

  5. The effect of water displacement on binding thermodynamics: concanavalin A.

    PubMed

    Li, Zheng; Lazaridis, Themis

    2005-01-13

    Interactions at the binding interface of biomolecular complexes are often mediated by ordered water molecules. In this work, we considered two concanavalin A-carbohydrate complexes. In the first, a water molecule is buried at the binding interface. In the second, this water molecule is displaced by a modification of the ligand (Clarke, C.; Woods, R. J.; Gluska, J.; Cooper, A.; Nutley, M. A.; Boons, G. J. J. Am. Chem. Soc. 2001, 123, 12238-12247). We computed the contribution of this water molecule to the thermodynamic properties using statistical mechanical formulas for the energy and entropy and molecular dynamics simulations. Other contributions to the binding affinity, including desolvation, entropy of conformational restriction, and interaction between the ligand and protein, were also computed. The thermodynamic consequences of displacement of the ordered water molecule by ligand modification were in qualitative agreement with experimental data. The free energy contribution of the water molecule (-17.2 kcal/mol; -19.2 enthalpic and +2 entropic) was nearly equivalent to the additional protein-ligand interactions in trimannoside 2 (-18.9 kcal/mol). The two structural ions interact more strongly with the water than with the hydroxyl of trimannoside 2, thus favoring trimannoside 1. The contributions from desolvation and conformational entropy are much smaller but significant, compared to the binding free energy difference. The picture that emerges is that the final outcome of water displacement is sensitive to the details of the binding site and cannot be predicted by simple empirical rules.

  6. 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)].

  7. 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.

  8. Revisiting the effect of colonial institutions on comparative economic development.

    PubMed

    Assenova, Valentina A; Regele, Matthew

    2017-01-01

    European settler mortality has been proposed as an instrument to predict the causal effect of colonial institutions on differences in economic development. We examine the relationship between mortality, temperature, and economic development in former European colonies in Asia, Africa, and the Americas. We find that (i) European settler mortality rates increased with regional temperatures and (ii) economic output decreased with regional temperatures. Conditioning on the continent of settlement and accounting for colonies that were not independent as of 1900 undermines the causal effect of colonial institutions on comparative economic development. Our findings run counter to the institutions hypothesis of economic development, showing instead that geography affected both historic mortality rates and present-day economic output.

  9. Revisiting the mitogenetic effect of ultra-weak photon emission

    PubMed Central

    Volodyaev, Ilya; Beloussov, Lev V.

    2015-01-01

    This paper reviews the 90 years long controversial history of the so-called “mitogenetic radiation,” the first case of non-chemical distant interactions, reported by Gurwitsch (1923). It was soon described as ultraweak UV, emitted by a number of biological systems, and stimulating mitosis in “competent” (in this sense) cells. In the following 20 years this phenomenon attracted enormous interest of the scientific community, and gave rise to more than 700 publications around the world. Yet, this wave of research vanished after several ostensibly disproving works in late 1930-s, and was not resumed later, regardless of quite serious grounds for that. The authors discuss separately two aspects of the problem: (1) do living organisms emit ultraweak radiation in the UV range (irrespective of whether it has any biological role), and (2) are there any real effects of this ultraweak photon emission (UPE) upon cell division and/or other biological functions? Analysis of the available data permits to conclude, that UV fraction of UPE should be regarded real, while its biological effects are difficult to reproduce. This causes a paradox. A number of presently known qualities of UPE were initially discovered (predicted?) by the “early workers” on the basis of biological effects. Yet the qualities they discovered were proved later (the UV component of UPE, the sources of UPE among biological systems, etc…), while the biological effect they used for UPE “detection” remains questionable. Importance of this area for basic biology and medicine, and potential usefulness of UPE as a non-invasive research method, invite scientists to attack this problem again, applying powerful research facilities of modern science. Yet, because of complexity and uncertainty of the problem, further progress in this area demands comprehensive examination of both positive and negative works, with particular attention to their methodical details. PMID:26441668

  10. Revisiting the "Christmas Holiday Effect" in the Southern Hemisphere.

    PubMed

    Knight, Josh; Schilling, Chris; Barnett, Adrian; Jackson, Rod; Clarke, Phillip

    2016-12-22

    A "Christmas holiday effect" showing elevated cardiovascular mortality over the Christmas holidays (December 25 to January 7) was demonstrated previously in study from the United States. To separate the effect of seasonality from any holiday effect, a matching analysis was conducted for New Zealand, where the Christmas holiday period falls within the summer season. New Zealand mortality data for a 25-year period (1988-2013) was analyzed based on the same methodology used in the previous study. Locally weighted smoothing was used to calculate an "expected" number of deaths for each day of the year. The expected value was compared with the actual number of deaths. In addition, mean age at death was estimated and used to assess the life-years lost due to excess mortality. There were 738 409 deaths (197 109 coded as cardiac deaths) during the period. We found evidence of a Christmas holiday effect in our of medical facility's cardiac deaths, with an excess event rate of 4.2% (95% CI 0.7-7.7%) leading to ≈4 additional deaths per annum. The average age of those with fatal cardiac deaths was 76.8 years (SD 13.5) during the Christmas holiday period, resulting in 148 to 222 years of life lost per annum. Cardiac mortality is elevated during the Christmas holiday period relative to surrounding time periods. Our findings are consistent with a previously reported study conducted in the United States, suggesting that cardiac mortality does not take a "summer break." © 2016 The Authors. Published on behalf of the American Heart Association, Inc., by Wiley Blackwell.

  11. 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.

  12. 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.

  13. The case of the Doppler effect for photons revisited

    NASA Astrophysics Data System (ADS)

    Redžić, Dragan V.

    2013-11-01

    A detailed account is presented of the Doppler effect as a photon phenomenon, complementing a recent paper by Giuliani (2013 Eur. J. Phys. 34 1035-47). The essence of Schrödinger's pioneering derivation (1922 Phys. Z. 23 301-3) of a Doppler formula in terms of the corpuscular theory of light, using energy-momentum conservation, is related. Some neglected references that put the whole scene around the Ives-Stilwell experiment into a more precise perspective are highlighted. Atoms as clocks and particle-wave complementarity are also discussed briefly.

  14. 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.

  15. 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.

  16. 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.

  17. Revisiting the Effect of Nicotine on Interval Timing

    PubMed Central

    Daniels, Carter W.; Watterson, Elizabeth; Garcia, Raul; Mazur, Gabriel J.; Brackney, Ryan J.; Sanabria, Federico

    2015-01-01

    This paper reviews the evidence for nicotine-induced acceleration of the internal clock when timing in the seconds-to-minutes timescale, and proposes an alternative explanation to this evidence: that nicotine reduces the threshold for responses that result in more reinforcement. These two hypotheses were tested in male Wistar rats using a novel timing task. In this task, rats were trained to seek food at one location after 8 s since trial onset and at a different location after 16 s. Some rats received the same reward at both times (group SAME); some received a larger reward at 16 s (group DIFF). Steady baseline performance was followed by 3 days of subcutaneous nicotine administration (0.3 mg/kg), baseline recovery, and an antagonist challenge (mecamylamine, 1.0 mg/kg). Nicotine induced a larger, immediate reduction in latencies to switch (LTS) in group DIFF than in group SAME. This effect was sustained throughout nicotine administration. Mecamylamine administration and discontinuation of nicotine rapidly recovered baseline performance. These results support a response-threshold account of nicotinic disruption of timing performance, possibly mediated by nicotinic acetylcholine receptors. A detailed analysis of the distribution of LTSs suggests that anomalous effects of nicotine on LTS dispersion may be due to loss of temporal control of behavior. PMID:25637907

  18. 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.

  19. 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.

  20. 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.

  1. Vectorlike fermions and Higgs effective field theory revisited

    DOE PAGES

    Chen, Chien-Yi; Dawson, S.; Furlan, Elisabetta

    2017-07-10

    Heavy vectorlike quarks (VLQs) appear in many models of beyond the Standard Model physics. Direct experimental searches require these new quarks to be heavy, ≳ 800 – 1000 GeV . Here, we perform a global fit of the parameters of simple VLQ models in minimal representations of S U ( 2 ) L to precision data and Higgs rates. One interesting connection between anomalous Z bmore » $$\\bar{b}$$ interactions and Higgs physics in VLQ models is discussed. Finally, we present our analysis in an effective field theory (EFT) framework and show that the parameters of VLQ models are already highly constrained. Exact and approximate analytical formulas for the S and T parameters in the VLQ models we consider are available in the Supplemental Material as Mathematica files.« less

  2. Vectorlike fermions and Higgs effective field theory revisited

    NASA Astrophysics Data System (ADS)

    Chen, Chien-Yi; Dawson, S.; Furlan, Elisabetta

    2017-07-01

    Heavy vectorlike quarks (VLQs) appear in many models of beyond the Standard Model physics. Direct experimental searches require these new quarks to be heavy, ≳800 - 1000 GeV . We perform a global fit of the parameters of simple VLQ models in minimal representations of S U (2 )L to precision data and Higgs rates. An interesting connection between anomalous Z b b ¯ interactions and Higgs physics in VLQ models is discussed. Finally, we present our analysis in an effective field theory (EFT) framework and show that the parameters of VLQ models are already highly constrained. Exact and approximate analytical formulas for the S and T parameters in the VLQ models we consider are available in the Supplemental Material as Mathematica files.

  3. 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.

  4. Nutrigenomics in cancer: Revisiting the effects of natural compounds.

    PubMed

    Braicu, Cornelia; Mehterov, Nikolay; Vladimirov, Boyan; Sarafian, Victoria; Nabavi, Seyed Mohammad; Atanasov, Atanas G; Berindan-Neagoe, Ioana

    2017-07-01

    Nutrigenomics effects have an important role in the manipulation of dietary components for human benefit, particularly in cancer prevention or treatment. The impact of dietary components, including phytochemicals, is largely studied by nutrigenomics, looking at the gene expression and molecular mechanisms interacting with bioactive compounds and nutrients, based on new 'omics' technologies. The high number of preclinical studies proves the relevant role of nutrigenomics in cancer management. By deciphering the network of nutrient-gene connections associated with cancer, relevant data will be transposed as therapeutic interventions for this devastating pathology and for fulfilling the concept of personalized nutrition. All these are presented under the nutrigenomics canopy for a better comprehension of the relation between ingested phytochemicals and chemoprevention or chemotherapy. The profits from the nutrigenomics progress, with a particular focus on the coding and noncoding genes related to the exposure of natural compounds need to be validated. A precise attention receives the evaluation of the role of natural compounds in tandem with conventional therapy using genomic approaches, with emphasis on the capacity to inhibit drug resistance mechanisms. All these relevant nutrigenomics aspects are summarized in the present review paper. It is concluded that further nutrigenomics studies are required to improve our understanding related to the complex mechanisms of action of the natural compounds and for their appropriate application as gears in cancer therapy. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. 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

  6. Quantum gravity effects on the thermodynamic stability of 4D Schwarzschild black hole

    NASA Astrophysics Data System (ADS)

    El-Menoufi, Basem Kamal

    2017-08-01

    Based on the Euclidean approach, we consider the effects of quantum gravity and mass-less matter on the thermodynamic properties of Schwarzschild black hole. The techniques of effective field theory are utilized to analytically construct the partition function at the one-loop level. Using the non-local heat kernel formalism, the partition function is expressed as a curvature expansion. We extensively discuss the effect of the corrections on the thermodynamic stability. The one-loop free energy shows, remarkably, that a large number of gauge fields is able to render Schwarzschild black hole thermodynamically stable. The black hole mass at which stability is achieved scales as √{N} in Planck units, where N is the number of gauge fields, and is independent of any UV completion of quantum gravity.

  7. 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

  8. 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.

  9. Non-equilibrium thermodynamic effects during cell division

    NASA Astrophysics Data System (ADS)

    Jose, Jorge

    2009-03-01

    A mitotic spindle is a regular structure within a cell consisting of oriented microtubule fibers. It plays a fundamental role in chromosome separation during cell division. Forming a spindle pattern is a major structural step towards mitosis. We have developed biophysical non-equilibrium thermodynamic models to describe in vitro chromosome driven spindle formation experiments in Xenopus extracts. Our first 2D model calculations [1] successfully described the order of events seen in some of the Xenopus extracts experiments, where the chromosomes are replaced by chromatin-covered micrometer magnetic beads. I will describe more realistic 3D improvements in our modeling analysis, which include microtubule contact forces and excluded volume [2, 3]. There are, however, a number of challenges that must be addressed for spindle modeling to continue to be a useful tool for understanding this fundamental biological process, in particular the biophysical simulation times. In this talk I will describe some important problems needing better biological data and hypothesis. I will also discuss our most recent numerical algorithmic improvements that are expected to greatly increase the simulations speed and thus allowing a more realistic representation of the experimental situation in Xenopus extracts. [1] S. C. Schaffner and J. V. Jose, PNAS, 103, 11166 (2006), [2] ibid in ``Methods in Cell Biology'' (Elsevier- Academic Press)(2008)and [3]ibid(to be published).

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. Intrafusal effects of botulinum toxin injections for spasticity: revisiting a previous paper.

    PubMed

    Phadke, Chetan P; On, Arzu Y; Kirazli, Yesim; Ismail, Farooq; Boulias, Chris

    2013-04-29

    Botulinum toxin, frequently used to manage focal limb spasticity, has been reported to affect both extrafusal and intrafusal fibers of the injected muscle. Since most studies have used spinal reflexes, it is difficult to isolate the intrafusal effects from extrafusal and central effects. In a paper by On et al. [7], both stretch and H-reflexes were used to examine the intrafusal effects of botulinum toxin injections. Revisiting the data from On et al. [7] presented a unique opportunity to describe a novel method of measuring the effect of botulinum toxin-A on muscle spindle activity in patients with spasticity. H-reflex, maximum M-wave, and Achilles tendon reflex were serially assessed in ten patients with stroke pre-, 2, 4, and 12 weeks post-botulinum. In order to assess the intrafusal effects, we subtracted the %change in H-reflex amplitude from baseline (representing extrafusal and central effects) from the %change in Achilles tendon reflex amplitude from baseline (representing intrafusal, extrafusal and central effects). Using this formula, our results suggest that botulinum induces significant chemodenervation of the intrafusal muscle fibers (33% decreases). Intrafusal effects were greatest at 2 weeks, but tapered off by 12 weeks post-botulinum (p<0.017). We found a significant positive correlation between the intrafusal effects of botulinum toxin and changes in modified Ashworth scale. Our method of assessing the effects of botulinum toxin shows significant effect on intrafusal fibers, which correlates with clinical manifestation of spasticity. Future studies need to investigate ways to maximize intrafusal effects and minimize extrafusal effects of botulinum therapy. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

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

    USDA-ARS?s Scientific Manuscript database

    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 ...

  16. 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…

  17. 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…

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. Low Reynolds Flow Visualization Revisited: Free-Surface and Wall Effects

    NASA Astrophysics Data System (ADS)

    Chan, Shelley; Sznitman, Josue; Smits, Alexander

    2009-11-01

    Many of the seminal experimental flow visualizations at low Reynolds number can be attributed to the pioneering works of S. Taneda. These classic investigations are still considered today benchmark visualizations and are widely used as textbook examples (Van Dyke, An Album of Fluid Motion, 1982). With the advent of modern quantitative flow visualization techniques, we are in a position to revisit in more detail some of the original questions posed by Taneda, including boundary effects on viscous flows surrounding objects (J Phys Soc Jpn, 1964). In the present talk, we conduct experimental flow visualizations around three-dimensional objects at low Reynolds number (Re=O(10-3-10-1)). Quantitative visualizations are implemented in a tow tank using velocimetry measurements (PIV); models including cubes and spheres are submerged in a highly viscous Newtonian fluid (silicon oil, 5000x viscosity of water). Here, we discuss wall effects on velocity profiles in the near- and far-field surrounding such objects. Moreover, we interrogate the influence of the free surface of the tank on the resulting viscous flow fields. The present experimental setup offers a versatile framework to investigate a wide range of fundamental fluid mechanical problems relating flows at low Reynolds number.

  3. 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.

  4. 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’.

  5. 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

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

    PubMed Central

    Castán, Teresa; Saxena, Avadh

    2016-01-01

    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’. PMID:27402925

  7. 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’.

  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'. © 2016 The Author(s).

  9. 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.

  10. Revisiting the decoupling effects in the running of the Cosmological Constant

    NASA Astrophysics Data System (ADS)

    Antipin, Oleg; Melić, Blaženka

    2017-09-01

    We revisit the decoupling effects associated with heavy particles in the renormalization group running of the vacuum energy in a mass-dependent renormalization scheme. We find the running of the vacuum energy stemming from the Higgs condensate in the entire energy range and show that it behaves as expected from the simple dimensional arguments meaning that it exhibits the quadratic sensitivity to the mass of the heavy particles in the infrared regime. The consequence of such a running to the fine-tuning problem with the measured value of the Cosmological Constant is analyzed and the constraint on the mass spectrum of a given model is derived. We show that in the Standard Model (SM) this fine-tuning constraint is not satisfied while in the massless theories this constraint formally coincides with the well known Veltman condition. We also provide a remarkably simple extension of the SM where saturation of this constraint enables us to predict the radiative Higgs mass correctly. Generalization to constant curvature spaces is also given.

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

    PubMed

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

    2015-12-01

    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.

  12. 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

  13. 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.

  14. 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. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.

  15. 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.

  16. 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

    2017-03-29

    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.

  17. Effect of dissociation on thermodynamic properties of pure diatomic gases

    NASA Technical Reports Server (NTRS)

    Woolley, Harold W

    1955-01-01

    A graphical method is described by which the enthalpy, entropy, and compressibility factor for the equilibrium mixture of atoms and diatomic molecules for pure gaseous elements may be obtained and shown for any dissociating element for which the necessary data exist. Results are given for hydrogen, oxygen, and nitrogen. The effect of dissociation on the heat capacity is discussed briefly.

  18. Positional and neighboring base pair effects on the thermodynamic stability of RNA single mismatches.

    PubMed

    Davis, Amber R; Znosko, Brent M

    2010-10-12

    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 for predicting the 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 the 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 have allowed for the investigation of these effects. The thermodynamic contributions of 13 single mismatch-nearest neighbor combinations are reported, but only nine 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 the single mismatch position in the duplex. The prediction algorithm recently proposed by Davis and Znosko [Davis, A. R., and Znosko, B. M. (2008) Biochemistry 47, 10178-10187] is used to predict the thermodynamic parameters of single mismatch contribution, and those values are compared to the measured values presented here. This comparison suggests the proposed model is a good approximation but could be improved by

  19. 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.

  20. 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…

  1. 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…

  2. 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.

  3. 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.

  4. Brush effects on DNA chips: thermodynamics, kinetics, and design guidelines.

    PubMed

    Halperin, A; Buhot, A; Zhulina, E B

    2005-08-01

    In biology experiments, oligonucleotide microarrays are contacted with a solution of long nucleic acid targets. The hybridized probes thus carry long tails. When the surface density of the oligonucleotide probes is high enough, the progress of hybridization gives rise to a polyelectrolyte brush due to mutual crowding of the nucleic acid tails. The free-energy penalty associated with the brush modifies both the hybridization isotherms and the rate equations: the attainable hybridization is lowered significantly as is the hybridization rate. When the equilibrium hybridization fraction, x(eq), is low, the hybridization follows a Langmuir type isotherm, x(eq)/(1 - x(eq)) = c(t)K where c(t) is the target concentration and K is the equilibrium constant. K is smaller than its bulk value by a factor (n/N)(2/5) due to wall effects where n and N denote the number of bases in the probe and the target. At higher x(eq), when the brush is formed, the leading correction is x(eq)/(1 - x(eq)) = c(t)K exp - const'x(eq)(2/3) - x(B)(2/3) where x(B) corresponds to the onset of the brush regime. The denaturation rate constant in the two regimes is identical. However, the hybridization rate constant in the brush regime is lower, the leading correction being exp -const' x(2/3) - x(B)(2/3).

  5. 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.

  6. 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.

  7. 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

  8. 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.

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

    PubMed

    Vieira, N S M; Luís, A; 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

    2016-06-01

    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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. Effects of thermodynamic profiles on the interaction of binary tropical cyclones

    NASA Astrophysics Data System (ADS)

    Jang, Wook; Chun, Hye-Yeong

    2015-09-01

    The interactions between idealized binary tropical cyclones (TCs) on f and β planes with different separation distance and thermodynamic soundings obtained from the National Centers for Environmental Prediction/National Center for Atmospheric Research reanalysis data averaged over the western North Pacific are investigated through ensemble three-dimensional numerical simulations with a horizontal resolution of 10 km in a single domain. In the simulations on the f plane, two TCs show mutual cyclonic rotations with symmetric structures. Two TCs with thermodynamic profiles of larger convective available potential energy (CAPE) and maximum potential intensity (MPI) show greater interaction than those with a smaller CAPE and MPI due to the stronger tangential velocity near the TC center. In the simulations on the β plane, the two TCs do not merge, because the beta effect prevents the attraction of the two TCs by generating asymmetric motions of the TC with northwestward forcing. The relative strengths of the two TCs change with time and depend on the low-level inflow influenced by the Coriolis parameter. Similar to the results on the f plane, the two TCs only merge with the thermodynamic soundings of large CAPE and MPI.

  15. 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

  16. 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.

  17. 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

  18. 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.

  19. Energy effects on the structure and thermodynamic properties of nanoconfined fluids (a density functional theory study).

    PubMed

    Keshavarzi, Ezat; Kamalvand, Mohammad

    2009-04-23

    The structure and properties of fluids confined in nanopores may show a dramatic departure from macroscopic bulk fluids. The main reason for this difference lies in the influence of system walls. In addition to the entropic wall effect, system walls can significantly change the energy of the confined fluid compared to macroscopic bulk fluids. The energy effect of the walls on a nanoconfined fluid appears in two forms. The first effect is the cutting off of the intermolecular interactions by the walls, which appears for example in the integrals for calculation of the thermodynamic properties. The second wall effect involves the wall-molecule interactions. In such confined fluids, the introduction of wall forces and the competition between fluid-wall and fluid-fluid forces could lead to interesting thermodynamic properties, including new kinds of phase transitions not observed in the macroscopic fluid systems. In this article, we use the perturbative fundamental measure density functional theory to study energy effects on the structure and properties of a hard core two-Yukawa fluid confined in a nanoslit. Our results show the changes undergone by the structure and phase transition of the nanoconfined fluids as a result of energy effects.

  20. 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.

  1. 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)

  2. 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)

  3. 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.

  4. 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.

  5. Shaping the composition profiles in heteroepitaxial quantum dots: Interplay of thermodynamic and kinetic effects

    SciTech Connect

    Georgiou, C.; Leontiou, T.; Kelires, P. C.

    2014-07-15

    Atomistic Monte Carlo simulations, coupling thermodynamic and kinetic effects, resolve a longstanding controversy regarding the origin of composition profiles in heteroepitaxial SiGe quantum dots. It is shown that profiles with cores rich in the unstrained (Si) component derive from near-equilibrium processes and intraisland diffusion. Profiles with cores rich in the strained (Ge) component are of nonequilibrium nature, i.e., they are strain driven but kinetically limited. They are shaped by the distribution of kinetic barriers of atomic diffusion in the islands. The diffusion pathways are clearly revealed for the first time. Geometrical kinetics play a minor role.

  6. An effective-field theory study of trilayer Ising nanostructure: Thermodynamic and magnetic properties

    NASA Astrophysics Data System (ADS)

    Santos, Jander P.; Sá Barreto, F. C.

    2017-10-01

    Thermodynamic and magnetic properties of a trilayer nanostructure of hexagonal lattices described by the spin-1/2 Ising model are investigated by the use of the effective-field theory (EFT) with correlations. The results for the magnetization, the free energy, the internal energy, the entropy, the specific heat and the critical frontiers were obtained. The critical temperature and the compensation temperature are investigated with a negative interlayer coupling, in order to clarify the distinction between the ferromagnetic and ferrimagnetic behaviors. From the thermal variations of the total magnetization, the six compensation types can be found, i.e., L-, Q-, R-, S-, P-, and N-types.

  7. 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.

  8. 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.

  9. 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

  10. Whole-Genome Thermodynamic Analysis Reduces siRNA Off-Target Effects

    PubMed Central

    Chen, Xi; Liu, Peng; Chou, Hui-Hsien

    2013-01-01

    Small interfering RNAs (siRNAs) are important tools for knocking down targeted genes, and have been widely applied to biological and biomedical research. To design siRNAs, two important aspects must be considered: the potency in knocking down target genes and the off-target effect on any nontarget genes. Although many studies have produced useful tools to design potent siRNAs, off-target prevention has mostly been delegated to sequence-level alignment tools such as BLAST. We hypothesize that whole-genome thermodynamic analysis can identify potential off-targets with higher precision and help us avoid siRNAs that may have strong off-target effects. To validate this hypothesis, two siRNA sets were designed to target three human genes IDH1, ITPR2 and TRIM28. They were selected from the output of two popular siRNA design tools, siDirect and siDesign. Both siRNA design tools have incorporated sequence-level screening to avoid off-targets, thus their output is believed to be optimal. However, one of the sets we tested has off-target genes predicted by Picky, a whole-genome thermodynamic analysis tool. Picky can identify off-target genes that may hybridize to a siRNA within a user-specified melting temperature range. Our experiments validated that some off-target genes predicted by Picky can indeed be inhibited by siRNAs. Similar experiments were performed using commercially available siRNAs and a few off-target genes were also found to be inhibited as predicted by Picky. In summary, we demonstrate that whole-genome thermodynamic analysis can identify off-target genes that are missed in sequence-level screening. Because Picky prediction is deterministic according to thermodynamics, if a siRNA candidate has no Picky predicted off-targets, it is unlikely to cause off-target effects. Therefore, we recommend including Picky as an additional screening step in siRNA design. PMID:23484018

  11. Effects of thermodynamic inhibitors on the dissociation of methane hydrate: a molecular dynamics study.

    PubMed

    Yagasaki, Takuma; Matsumoto, Masakazu; Tanaka, Hideki

    2015-12-28

    We investigate the effects of methanol and NaCl, which are known as thermodynamic hydrate inhibitors, on the dissociation kinetics of methane hydrate in aqueous solutions by using molecular dynamics simulations. It is shown that the dissociation rate is not constant but changes with time. The dissociation rate in the initial stage is increased by methanol whereas it is decreased by NaCl. This difference arises from the opposite effects of the two thermodynamic inhibitors on the hydration free energy of methane. The dissociation rate of methane hydrate is increased by the formation of methane bubbles in the aqueous phase because the bubbles absorb surrounding methane molecules. It is found that both methanol and NaCl facilitate the bubble formation. However, their mechanisms are completely different from each other. The presence of ions enhances the hydrophobic interactions between methane molecules. In addition, the ions in the solution cause a highly non-uniform distribution of dissolved methane molecules. These two effects result in the easy formation of bubbles in the NaCl solution. In contrast, methanol assists the bubble formation because of its amphiphilic character.

  12. Thermodynamically consistent Langevin dynamics with spatially correlated noise predicting frictionless regime and transient attraction effect

    NASA Astrophysics Data System (ADS)

    Majka, M.; Góra, P. F.

    2016-10-01

    While the origins of temporal correlations in Langevin dynamics have been thoroughly researched, the understanding of spatially correlated noise (SCN) is rather incomplete. In particular, very little is known about the relation between friction and SCN. In this article, starting from the microscopic, deterministic model, we derive the analytical formula for the spatial correlation function in the particle-bath interactions. This expression shows that SCN is the inherent component of binary mixtures, originating from the effective (entropic) interactions. Further, employing this spatial correlation function, we postulate the thermodynamically consistent Langevin equation driven by the Gaussian SCN and calculate the adequate fluctuation-dissipation relation. The thermodynamical consistency is achieved by introducing the spatially variant friction coefficient, which can be also derived analytically. This coefficient exhibits a number of intriguing properties, e.g., the singular behavior for certain types of interactions. Eventually, we apply this new theory to the system of two charged particles in the presence of counter-ions. Such particles interact via the screened-charge Yukawa potential and the inclusion of SCN leads to the emergence of the anomalous frictionless regime. In this regime the particles can experience active propulsion leading to the transient attraction effect. This effect suggests a nonequilibrium mechanism facilitating the molecular binding of the like-charged particles.

  13. 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.

  14. Thermodynamically consistent Langevin dynamics with spatially correlated noise predicting frictionless regime and transient attraction effect.

    PubMed

    Majka, M; Góra, P F

    2016-10-01

    While the origins of temporal correlations in Langevin dynamics have been thoroughly researched, the understanding of spatially correlated noise (SCN) is rather incomplete. In particular, very little is known about the relation between friction and SCN. In this article, starting from the microscopic, deterministic model, we derive the analytical formula for the spatial correlation function in the particle-bath interactions. This expression shows that SCN is the inherent component of binary mixtures, originating from the effective (entropic) interactions. Further, employing this spatial correlation function, we postulate the thermodynamically consistent Langevin equation driven by the Gaussian SCN and calculate the adequate fluctuation-dissipation relation. The thermodynamical consistency is achieved by introducing the spatially variant friction coefficient, which can be also derived analytically. This coefficient exhibits a number of intriguing properties, e.g., the singular behavior for certain types of interactions. Eventually, we apply this new theory to the system of two charged particles in the presence of counter-ions. Such particles interact via the screened-charge Yukawa potential and the inclusion of SCN leads to the emergence of the anomalous frictionless regime. In this regime the particles can experience active propulsion leading to the transient attraction effect. This effect suggests a nonequilibrium mechanism facilitating the molecular binding of the like-charged particles.

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

    SciTech Connect

    Zhang, Chen; Liu, Hong

    2016-06-15

    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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  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. 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].

  2. Accelerating equilibrium isotope effect calculations. I. Stochastic thermodynamic integration with respect to mass

    NASA Astrophysics Data System (ADS)

    Karandashev, Konstantin; Vaníček, Jiří

    2017-05-01

    Accurate path integral Monte Carlo or molecular dynamics calculations of isotope effects have until recently been expensive because of the necessity to reduce three types of errors present in such calculations: statistical errors due to sampling, path integral discretization errors, and thermodynamic integration errors. While the statistical errors can be reduced with virial estimators and path integral discretization errors with high-order factorization of the Boltzmann operator, here we propose a method for accelerating isotope effect calculations by eliminating the integration error. We show that the integration error can be removed entirely by changing particle masses stochastically during the calculation and by using a piecewise linear umbrella biasing potential. Moreover, we demonstrate numerically that this approach does not increase the statistical error. The resulting acceleration of isotope effect calculations is demonstrated on a model harmonic system and on deuterated species of methane.

  3. 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

  4. 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.

  5. 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.

  6. An engineering thermodynamic approach to select the electromagnetic wave effective on cell growth.

    PubMed

    Lucia, Umberto; Grisolia, Giulia; Ponzetto, Antonio; Silvagno, Francesca

    2017-09-21

    To date, the choice of the characteristics of the extremely low-frequency electromagnetic field beneficial in proliferative disorders is still empirical. In order to make the ELF interaction selective, we applied the thermodynamic and biochemical principles to the analysis of the thermo-chemical output generated by the cell in the environment. The theoretical approach applied an engineering bio-thermodynamic approach recently developed in order to obtain a physical-mathematical model that calculated the frequency of the field able to maximize the mean entropy changes as a function of cellular parameters. The combined biochemical approach envisioned the changes of entropy as a metabolic shift leading to a reduction of cell growth. The proliferation of six human cancer cell lines was evaluated as the output signal able to confirm the correctness of the mathematical model. By considering the cell as a reactive system able to respond to the unbalancing external stimuli, for the first time we could calculate and validate the frequencies of the field specifically effective on distinct cells. Copyright © 2017 Elsevier Ltd. All rights reserved.

  7. 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.

  8. Molecular crowding has no effect on the dilution thermodynamics of the biologically relevant cation mixtures.

    PubMed

    Głogocka, Daria; Przybyło, Magdalena; Langner, Marek

    2017-04-01

    The ionic composition of intracellular space is rigorously maintained in the expense of high-energy expenditure. It has been recently postulated that the cytoplasmic ionic composition is optimized so the energy cost of the fluctuations of calcium ion concentration is minimized. Specifically, thermodynamic arguments have been produced to show that the presence of potassium ions at concentrations higher than 100 mM reduce extend of the energy dissipation required for the dilution of calcium cations. No such effect has been measured when sodium ions were present in the solution or when the other divalent cation magnesium was diluted. The experimental observation has been interpreted as the indication of the formation of ionic clusters composed of calcium, chloride and potassium. In order to test the possibility that such clusters may be preserved in biological space, the thermodynamics of ionic mixtures dilution in solutions containing albumins and model lipid bilayers have been measured. Obtained thermograms clearly demonstrate that the energetics of calcium/potassium mixture is qualitatively different from calcium/sodium mixture indicating that the presence of the biologically relevant quantities of proteins and membrane hydrophilic surfaces do not interfere with the properties of the intracellular aqueous phase.

  9. 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.

  10. 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.

  11. 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.

  12. 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

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. Thermodynamic Diagrams

    NASA Astrophysics Data System (ADS)

    Chaston, Scot

    1999-02-01

    Thermodynamic data such as equilibrium constants, standard cell potentials, molar enthalpies of formation, and standard entropies of substances can be a very useful basis for an organized presentation of knowledge in diverse areas of applied chemistry. Thermodynamic data can become particularly useful when incorporated into thermodynamic diagrams that are designed to be easy to recall, to serve as a basis for reconstructing previous knowledge, and to determine whether reactions can occur exergonically or only with the help of an external energy source. Few students in our chemistry-based courses would want to acquire the depth of knowledge or rigor of professional thermodynamicists. But they should nevertheless learn how to make good use of thermodynamic data in their professional occupations that span the chemical, biological, environmental, and medical laboratory fields. This article discusses examples of three thermodynamic diagrams that have been developed for this purpose. They are the thermodynamic energy account (TEA), the total entropy scale, and the thermodynamic scale diagrams. These diagrams help in the teaching and learning of thermodynamics by bringing the imagination into the process of developing a better understanding of abstract thermodynamic functions, and by allowing the reader to keep track of specialist thermodynamic discourses in the literature.

  18. The Effects of Korean Medical Service Quality and Satisfaction on Revisit Intention of the United Arab Emirates Government Sponsored Patients.

    PubMed

    Lee, Seoyoung; Kim, Eun-Kyung

    2017-06-01

    The purpose of this study was to investigate medical service quality, satisfaction and to examine factors influencing hospital revisit intention of the United Arab Emirates government sponsored patients in Korea. A total of 152 UAE government sponsored patients who visited Korean hospitals participated in the questionnaire survey from August to November 2016. Stepwise multiple regression was used to identify the factors that affected the revisit intention of the participants. The mean scores of medical service quality, satisfaction, and revisit intention were 5.72 out of 7, 88.88 out of 100, 4.59 out of 5, respectively. Medical service quality and satisfaction, Medical service quality and revisit intention, satisfaction and revisit intention were positively correlated. Medical service of physician, visiting routes and responsiveness of medical service quality explained about 23.8% of revisit intention. There are needs for physicians to communicate with patients while ensuring sufficient consultation time based on excellent medical skills and nurses to respond immediately for the patients' needs through an empathic encounter in order to improve medical service quality and patient satisfaction so that to increase the revisit intention of the United Arab Emirates government sponsored patients. Further, it is necessary for the hospitals to have support plans for providing country specialized services in consideration of the UAE culture to ensure that physicians' and nurses' competencies are not undervalued by non-medical service elements such as interpreters and meals. Copyright © 2017. Published by Elsevier B.V.

  19. Thermodynamic and Electronic Properties of Liquid Binary Alloys of Simple Metals: Charge-Transfer Effects.

    NASA Astrophysics Data System (ADS)

    Lai, San-Kiong

    It is demonstrated that low order pseudopotential perturbation theory is inadequate to determine the equilibrium atomic volumes even for simple liquid metals and their alloys in variational thermodynamic calculations. A high order perturbative correction is suggested and has subsequently been applied in the spirit of the model pseudopotential theory. A theoretical method is proposed to determine a model potential parameter (denoted by (mu)) using the calculated unmodified ((mu) = 0) Helmholtz free energy. Results of the applications to the (i) excess entropy and (ii) isothermal compressibility indicate that the parameter (mu) is insignificant for the liquid alkali metals, Zn and Mg but becomes more important for such heavy elements as In. Based on this conclusion the calculations for the liquid alkali binary alloys are carried out by setting (mu) = 0. We apply our obtained hard sphere diameters to calculate the concentration dependences of (i) the isothermal compressibility, (ii) the excess entropy of mixing and (iii) the enthalpy and free energy of mixing within the framework of the hard sphere theory. Then, the anomalies of the thermodynamic mixing properties for these alloys, as experimentally reported, are interpreted by considering valence-electron charge transfer effects. The alloy formfactors have also been applied to study the electronic properties. Before embarking on the calculation, we first check the high-order effects on the electronic density of states. They are found to be unimportant for those liquid metals for which (mu)(, )<(, )0.1. Then, we set (mu) = 0 and study the concentration dependences of the (i) electron density of states, (ii) electrical resistivity and thermopower and (iii) temperature coefficient of the resistivity for the alkali, Li-Na and Li-Mg alloys. It also emerges from these applications that charge transfer effects, which give rise to the partial localisation of the valence electrons on the electronegative ions, are

  20. Revisiting the incremental effects of context on word processing: Evidence from single-word event-related brain potentials.

    PubMed

    Payne, Brennan R; Lee, Chia-Lin; Federmeier, Kara D

    2015-11-01

    The amplitude of the N400-an event-related potential (ERP) component linked to meaning processing and initial access to semantic memory-is inversely related to the incremental buildup of semantic context over the course of a sentence. We revisited the nature and scope of this incremental context effect, adopting a word-level linear mixed-effects modeling approach, with the goal of probing the continuous and incremental effects of semantic and syntactic context on multiple aspects of lexical processing during sentence comprehension (i.e., effects of word frequency and orthographic neighborhood). First, we replicated the classic word-position effect at the single-word level: Open-class words showed reductions in N400 amplitude with increasing word position in semantically congruent sentences only. Importantly, we found that accruing sentence context had separable influences on the effects of frequency and neighborhood on the N400. Word frequency effects were reduced with accumulating semantic context. However, orthographic neighborhood was unaffected by accumulating context, showing robust effects on the N400 across all words, even within congruent sentences. Additionally, we found that N400 amplitudes to closed-class words were reduced with incrementally constraining syntactic context in sentences that provided only syntactic constraints. Taken together, our findings indicate that modeling word-level variability in ERPs reveals mechanisms by which different sources of information simultaneously contribute to the unfolding neural dynamics of comprehension. © 2015 Society for Psychophysiological Research.

  1. Revisiting the Incremental Effects of Context on Word Processing: Evidence from Single-Word Event-Related Brain Potentials

    PubMed Central

    Payne, Brennan R.; Lee, Chia-Lin; Federmeier, Kara D.

    2015-01-01

    The amplitude of the N400— an event-related potential (ERP) component linked to meaning processing and initial access to semantic memory— is inversely related to the incremental build-up of semantic context over the course of a sentence. We revisited the nature and scope of this incremental context effect, adopting a word-level linear mixed-effects modeling approach, with the goal of probing the continuous and incremental effects of semantic and syntactic context on multiple aspects of lexical processing during sentence comprehension (i.e., effects of word frequency and orthographic neighborhood). First, we replicated the classic word position effect at the single-word level: open-class words showed reductions in N400 amplitude with increasing word position in semantically congruent sentences only. Importantly, we found that accruing sentence context had separable influences on the effects of frequency and neighborhood on the N400. Word frequency effects were reduced with accumulating semantic context. However, orthographic neighborhood was unaffected by accumulating context, showing robust effects on the N400 across all words, even within congruent sentences. Additionally, we found that N400 amplitudes to closed-class words were reduced with incrementally constraining syntactic context in sentences that provided only syntactic constraints. Taken together, our findings indicate that modeling word-level variability in ERPs reveals mechanisms by which different sources of information simultaneously contribute to the unfolding neural dynamics of comprehension. PMID:26311477

  2. Pressure effects on the thermodynamic and mechanical properties of zinc-blende ZnTe compound

    NASA Astrophysics Data System (ADS)

    Vu, Ha Thi-Thanh; Pham, Hanh Thi-Minh; Nguyen, Tuyen Viet; Ho, Hieu Khac

    2017-04-01

    In this paper, the moment method in statistical mechanics has been employed to study the pressure effects on thermodynamic and mechanical properties of zinc-blende zinc telluride using many-body potential. We have derived the analytical expressions of the pressure-dependent lattice parameter, volume compression as well as mean-square displacement of zinc-blende type compound. Numerical calculations performed for ZnTe compound up to 12 GPa are found to be in good and reasonable agreement with available experimental data as well as with previous theoretical studies. These results have been used to evaluate the bulk modulus and its first pressure derivative of ZnTe. The present moment method has taken into account the quantum zero-point vibrations at low temperature and the higher-order anharmonic terms in the atomic displacements. This research shows the advantage of moment method on extensively studying thermo-mechanical properties of materials under high pressures.

  3. 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.

  4. 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.

  5. 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.

  6. 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).

  7. 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.

  8. 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

  9. Competition between rhythmic and linguistic meaning revisited: the effect of task demands.

    PubMed

    Getz, Laura M; Wohltjen, Sophie; Kubovy, Michael

    2017-07-01

    This paper revisits the conclusion of our previous work regarding the dominance of meaning in the competition between rhythmic parsing and linguistic parsing. We played five-note rhythm patterns in which each sound is a spoken word of a five-word sentence. We asked listeners to indicate the starting point of the rhythm while disregarding which word would normally be heard as the first word of the sentence. In four studies, we varied task demands by introducing differences in rhythm complexity, rhythm ambiguity, rhythm pairing, and semantic coherence. We found that task complexity affects the dominance of meaning. We therefore amend our previous conclusion: when processing resources are taxed, listeners do not always primarily attend to meaning; instead, they primarily attend to the aspect of the pattern (rhythm or meaning) that is more salient.

  10. Size effect on thermodynamic properties of CaMoO4 micro/nano materials and reaction systems

    NASA Astrophysics Data System (ADS)

    Fan, Gaochao; Huang, Zaiyin; Wang, Tenghui

    2013-02-01

    CaMoO4 micro/nano hollow spheres with three different sizes were prepared via a reverse-microemulsion route at room temperature. Through designing a novel thermochemical cycle, the relationship between thermodynamic properties of nano CaMoO4 and bulk CaMoO4 was built. Combined with in situ microcalorimetry, change regularities for the thermodynamic properties of the prepared CaMoO4 micro/nano materials and reaction systems were obtained. The results reveal that size effect has significant influence on thermodynamic properties of micro/nano materials and reaction systems. Along with the size decreasing, the standard molar enthalpy, standard molar Gibbs free energy and standard molar entropy of reaction of micro/nano reaction systems decreased, but the standard molar enthalpy of formation, standard molar Gibbs free energy of formation and standard molar entropy of micro/nano materials increased.

  11. 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.

  12. 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.

  13. 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

  14. 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

  15. 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

  16. 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

  17. Numerical Approximation to the Thermodynamic Integrals

    NASA Astrophysics Data System (ADS)

    Johns, S. M.; Ellis, P. J.; Lattimer, J. M.

    1996-12-01

    We approximate boson thermodynamic integrals as polynomials in two variables chosen to give the correct limiting expansion and to smoothly interpolate into other regimes. With 10 free parameters, an accuracy of better than 0.009% is achieved for the pressure, internal energy density, and number density. We also revisit the fermion case, originally addressed by Eggleton, Faulkner, & Flannery (1973), and substantially improve the accuracy of their fits.

  18. 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

  19. 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.

  20. 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.

  1. 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

  2. Finite-size effects in surface tension: Thermodynamics and the Gaussian interface model

    NASA Astrophysics Data System (ADS)

    Gelfand, Martin P.; Fisher, Michael E.

    1988-09-01

    It has been suggested by Kayser that finite-size effects associated with capillary waves might play a significant role in some surface tension measurements; for capillary rise between plates a distance D apart, an effect varying as 1/ D and apparently observable in measurements, was proposed. In reconsidering this problem, one must analyze the thermodynamics of finite-size corrections to surface tension. In particular, one sees that capillary rise between plates does not measure the interfacial free energy density but, rather, a derivative of the interfacial free energy with respect to a system dimension. The quantity needed to draw definite conclusions, the “finite-size residual” free energy, can be calculated within the harmonic or Gaussian capillary wave model in d spatial dimensions with the aid of Poisson summation techniques and should yield the correct leading asymptotic behavior. For d=3 and experimentally relevant parameter values, the results are independent of the short-wavelength cutoff needed in the model and can be checked against the theory of conformai covariance at two-dimensional critical points. It is found that the finite-size effects in capillary-rise measurements of surface tension vary as 1/ D 2 (with a universal coefficient) but are too small to be seen in current experiments.

  3. Thermodynamic analysis of the effect of concentrated salts on protein interaction with hydrophobic and polysaccharide columns.

    PubMed

    Arakawa, T

    1986-07-01

    An attempt was made to explain the effect of concentrated salts on protein interaction with hydrophobic columns. From the previously observed results of preferential interactions for salting-out salts with proteins, it was shown that the free energy of the protein is increased by addition of the salts and this unfavorable free energy is smaller for the proteins bound to the columns because of their smaller surface area exposed to solvent; i.e., the bound form of the proteins is thermodynamically more stable. This explains the protein binding to the hydrophobic columns at high salt concentrations and the elution by decreasing the salt concentration. The unfavorable interaction free energy was greater for Na2SO4 or (NH4)2SO4 than for NaCl, which explains the stronger effect of the former salts on the protein binding to the columns. The observed favorable interaction between KSCN or guanidine hydrochloride and the proteins explains the decreasing effect of these salts on the protein binding to the hydrophobic columns.

  4. 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.

  5. 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

  6. 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.

  7. Wormholes and thermodynamics

    NASA Astrophysics Data System (ADS)

    González-Díaz, Pedro F.

    1996-07-01

    Hawking has recently pointed out that black holes cannot evaporate and disappear through wormholes because the entropy of a baby universe would not equal its size squared times some proportionality constant. In this report it is shown that multiply connected Euclidean wormhole spacetimes can be associated with nonlinear dynamic laws which are analogous to those of nonequilibrium thermodynamics, making plausible a full generalization of thermodynamics encompassing both nonequilibrium and gravitational effects. It is seen that both at equilibrium and out of it baby universe thermodynamics can provide the right relation between the size of the originating black hole and its entropy.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. Perceived parenting style and adolescent adjustment: revisiting directions of effects and the role of parental knowledge.

    PubMed

    Kerr, Margaret; Stattin, Håkan; Ozdemir, Metin

    2012-11-01

    In the present research on parenting and adolescent behavior, there is much focus on reciprocal, bidirectional, and transactional processes, but parenting-style research still adheres to a unidirectional perspective in which parents affect youth behavior but are unaffected by it. In addition, many of the most cited parenting-style studies have used measures of parental behavioral control that are questionable because they include measures of parental knowledge. The goals of this study were to determine whether including knowledge items might have affected results of past studies and to test the unidirectional assumption. Data were from 978 adolescents participating in a longitudinal study. Parenting-style and adolescent adjustment measures at 2 time points were used, with a 2-year interval between time points. A variety of internal and external adjustment measures were used. Results showed that including knowledge items in measures of parental behavioral control elevated links between behavioral control and adjustment. Thus, the results and conclusions of many of the most highly cited studies are likely to have been stronger than if the measures had focused strictly on parental behavior. In addition, adolescent adjustment predicted changes in authoritative and neglectful parenting styles more robustly than these styles predicted changes in adolescent adjustment. Adolescent adjustment also predicted changes in authoritativeness more robustly than authoritativeness predicted changes in adjustment. Thus, parenting style cannot be seen as independent of the adolescent. In summary, both the theoretical premises of parenting-style research and the prior findings should be revisited.

  14. Iron chelators in photodynamic therapy revisited: synergistic effect by novel highly active thiosemicarbazones.

    PubMed

    Mrozek-Wilczkiewicz, Anna; Serda, Maciej; Musiol, Robert; Malecki, Grzegorz; Szurko, Agnieszka; Muchowicz, Angelika; Golab, Jakub; Ratuszna, Alicja; Polanski, Jaroslaw

    2014-04-10

    In photodynamic therapy (PDT), a noninvasive anticancer treatment, visible light, is used as a magic bullet selectively destroying cancer cells by a photosensitizer that is nontoxic in the dark. Protoporphyrin IX (PpIX) is a natural photosensitizer synthesized in the cell, which is also a chelating agent that if bonded to Fe(2+) forms heme, a central component of hemoglobin. Therefore, xenobiotic iron chelators can disturb iron homeostasis, increasing the accumulation of PpIX, obstructing the last step of heme biosynthesis, and enhancing PDT efficiency. However, the attempts to use this promising idea have not proved to be hugely successful. Herein, we revisited this issue by analyzing the application of iron chelators highly toxic in the dark, which should have higher Fe(2+) affinity than the nontoxic chelators used so far. We have designed and prepared thiosemicarbazones (TSC) with the highest dark cellular cytotoxicity among TSCs ever reported. We demonstrate that compound 2 exerts powerful PDT enhancement when used in combination with 5-aminolevulinic acid (ALA), a precursor of PpIX.

  15. Iron Chelators in Photodynamic Therapy Revisited: Synergistic Effect by Novel Highly Active Thiosemicarbazones

    PubMed Central

    2014-01-01

    In photodynamic therapy (PDT), a noninvasive anticancer treatment, visible light, is used as a magic bullet selectively destroying cancer cells by a photosensitizer that is nontoxic in the dark. Protoporphyrin IX (PpIX) is a natural photosensitizer synthesized in the cell, which is also a chelating agent that if bonded to Fe2+ forms heme, a central component of hemoglobin. Therefore, xenobiotic iron chelators can disturb iron homeostasis, increasing the accumulation of PpIX, obstructing the last step of heme biosynthesis, and enhancing PDT efficiency. However, the attempts to use this promising idea have not proved to be hugely successful. Herein, we revisited this issue by analyzing the application of iron chelators highly toxic in the dark, which should have higher Fe2+ affinity than the nontoxic chelators used so far. We have designed and prepared thiosemicarbazones (TSC) with the highest dark cellular cytotoxicity among TSCs ever reported. We demonstrate that compound 2 exerts powerful PDT enhancement when used in combination with 5-aminolevulinic acid (ALA), a precursor of PpIX. PMID:24900837

  16. 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).

  17. 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.

  18. 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.

  19. 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

  20. 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

  1. 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.

  2. 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.

  3. 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).

  4. 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.

  5. 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%.

  6. Thermodynamic analysis of the effect of selective monodeamidation at asparagine 67 in ribonuclease A.

    PubMed Central

    Catanzano, F.; Graziano, G.; Capasso, S.; Barone, G.

    1997-01-01

    Selective deamidation of proteins and peptides is a reaction of great interest, both because it has a physiological role and because it can cause alteration in the biological activity, local folding, and overall stability of the protein. In order to evaluate the thermodynamic effects of this reaction in proteins, we investigated the temperature-induced denaturation of ribonuclease A derivatives in which asparagine 67 was selectively replaced by an aspartyl residue or an isoaspartyl residue, as a consequence of an in vitro deamidation reaction. Differential scanning calorimetry measurements were performed in the pH range 3.0-6.0, where the unfolding process is reversible, according to the reheating criterion used. It resulted that the monodeamidated forms have a different thermal stability with respect to the parent enzyme. In particular, the replacement of asparagine 67 with an isoaspartyl residue leads to a decrease of 6.3 degrees C of denaturation temperature and 65 kJ mol-1 of denaturation enthalpy at pH 5.0. These results are discussed and correlated to the X-ray three-dimensional structure of this derivative. The analysis leads to the conclusion that the difference in thermal stability between RNase A and (N67isoD)RNase A is due to enthalpic effects arising from the loss of two important hydrogen bonds in the loop containing residue 67, partially counterbalanced by entropic effects. Finally, the influence of cytidine-2'-monophosphate on the stability of the three ribonucleases at pH 5.0 is studied and explained in terms of its binding on the active site of ribonucleases. The analysis makes it possible to estimate the apparent binding constant and binding enthalpy for the three proteins. PMID:9260280

  7. Thermodynamic electrophilicity.

    PubMed

    Miranda-Quintana, Ramón Alain

    2017-06-07

    We revisit the electrophilicity index proposed by Parr et al., with special emphasis on the working equations used to calculate this descriptor. We show that the standard way to obtain this reactivity index (using the conceptual density functional theory formalism) leads to several issues. In this contribution, we propose to overcome these difficulties by making use of the finite temperature grand-canonical formalism. In this way, we not only bypass the characteristic inconsistencies of the zero temperature formulation but we are able to obtain a simple exact working equation for the electrophilicity in terms of electronic structure magnitudes.

  8. 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

  9. 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.

  10. On the Effectiveness of Nature-Inspired Metaheuristic Algorithms for Performing Phase Equilibrium Thermodynamic Calculations

    PubMed Central

    Fateen, Seif-Eddeen K.; Bonilla-Petriciolet, Adrian

    2014-01-01

    The search for reliable and efficient global optimization algorithms for solving phase stability and phase equilibrium problems in applied thermodynamics is an ongoing area of research. In this study, we evaluated and compared the reliability and efficiency of eight selected nature-inspired metaheuristic algorithms for solving difficult phase stability and phase equilibrium problems. These algorithms are the cuckoo search (CS), intelligent firefly (IFA), bat (BA), artificial bee colony (ABC), MAKHA, a hybrid between monkey algorithm and krill herd algorithm, covariance matrix adaptation evolution strategy (CMAES), magnetic charged system search (MCSS), and bare bones particle swarm optimization (BBPSO). The results clearly showed that CS is the most reliable of all methods as it successfully solved all thermodynamic problems tested in this study. CS proved to be a promising nature-inspired optimization method to perform applied thermodynamic calculations for process design. PMID:24967430

  11. 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.

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

    PubMed

    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

    2015-04-01

    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, Na2S and Na2SO4) 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 Na2SO4 and Na2S 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 PbSO4(s) at low temperatures (<1000 K). The equilibrium calculation prediction also suggested that SiO2, CaO, TiO2, and Al2O3 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 concentration of Si, Ca and Al-containing compounds in the sludge. These findings provide useful information for understanding the partitioning behavior of Pb, facilitating the development of strategies to control the volatilization of Pb during sludge incineration. Copyright © 2014 Elsevier Ltd. All rights reserved.

  13. Thermodynamic anomalous Hall effect in quantum oscillation regime in a semiconductor with low concentration of transition element impurities

    NASA Astrophysics Data System (ADS)

    Lonchakov, A. T.; Okulov, V. I.; Pamyatnykh, E. A.; Bobin, S. B.; Deryushkin, V. V.; Govorkova, T. E.; Neverov, V. N.; Paranchich, L. D.

    2017-10-01

    The given report is devoted to the study of anomalous Hall resistance of donor electron system of hybridized states of transition element impurities of low concentration in quantum oscillation regime. There presented theoretical description of predicted specific behaviors on the base of the ideas about thermodynamic anomalous Hall effect. In experiments on mercury selenide crystals with cobalt impurities of low concentration one revealed the quantum oscillations of anomalous contribution to the Hall resistance corresponding to the developed concepts.

  14. On the proof of the first Carnot theorem in thermodynamics

    NASA Astrophysics Data System (ADS)

    Morad, M. R.; Momeni, F.

    2013-11-01

    The proof of the first Carnot theorem in classical thermodynamics is revisited in this study. The underlying conditions of a general proof of this principle presented by Senft (1978 Phys. Educ. 13 35-37) are explored and discussed. These conditions are analysed in more detail using a physical description of heat and work to present a simpler proof of the first principle prior to using the violation of the second law of thermodynamics. Finally, a new simple proof is also presented based on Gibbs relation. This discussion will benefit the teaching of classical thermodynamics and promote better understanding of the proof of the first Carnot theorem in general form.

  15. Strain effects on the structural, magnetic, and thermodynamic properties of the Au(001)/Fe(001) interface from first principles

    NASA Astrophysics Data System (ADS)

    Benoit, Magali; Combe, Nicolas; Ponchet, Anne; Morillo, Joseph; Casanove, Marie-José

    2014-10-01

    The structural, magnetic, and thermodynamic properties of the Au(001)/Fe(001) interface are investigated as a function of the in-plane strain using density functional theory calculations for two different Au slab thicknesses: 2 and 8 monolayers. The structural and magnetic properties are analyzed by studying the interlayer distance in the direction perpendicular to the interface and the atomic magnetic moments of Fe atoms, as a function of the in-plane strain. The structural study evidences both the bulk elastic and surface and interface contributions. The atomic magnetic moments of Fe atoms are essentially dependent on their local environment (number and distance of the Fe first neighbors). Thermodynamic properties of the interface are investigated through the calculation of the interface energy and interface stress. These thermodynamic quantities are subsequently used in a simple model to evaluate the strain state of an ideal spherical symmetric Fe@Au core-shell nanoparticle. The surface elastic effects are found to be significant for nanoparticles of diameter smaller than ˜20 nm and predominant for diameters smaller than ˜2.3 nm. Interface elastic effects are weaker than surface elastic effects but can not be neglected for very small nanoparticles (≲1.9 nm) or for thin shells.

  16. 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

  17. Effect of heavy ion irradiation on thermodynamically equilibrium Zr-Excel alloy

    NASA Astrophysics Data System (ADS)

    Yu, Hongbing; Liang, Jianlie; Yao, Zhongwen; Kirk, Mark A.; Daymond, Mark R.

    2017-05-01

    The thermodynamically equilibrium state was achieved in a Zr-Sn-Nb-Mo alloy by long-term annealing at an intermediate temperature. The fcc intermetallic Zr(Mo, Nb)2 enriched with Fe was observed at the equilibrium state. In-situ 1 MeV Kr2+ heavy ion irradiation was performed in a TEM to study the stability of the intermetallic particles under irradiation and the effects of the intermetallic particle on the evolution of type dislocation loops at different temperatures from 80 to 550 °C. Chemi-STEM elemental maps were made at the same particles before and after irradiation up to 10 dpa. It was found that no elemental redistribution occurs at 200 °C and below. Selective depletion of Fe was observed from some precipitates under irradiation at higher temperatures. No change in the morphology of particles and no evidence showing a crystalline to amorphous transformation were observed at all irradiation temperatures. The formation of type dislocation loops was observed under irradiation at 80 and 200 °C, but not at 450 and 550 °C. The loops were non-uniformly distributed; a localized high density of type dislocation loops were observed near the second phase particles; we suggest that loop nucleation is favored as a result of the stress induced by the particles, rather than by elemental redistribution. The stability of the second phase particles and the formation of the type loops under heavy ion irradiation are discussed.

  18. 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.

  19. Effect of Mg Content on the Thermodynamics of Interface Reaction in Cf/Al Composite

    NASA Astrophysics Data System (ADS)

    Wang, Chenchong; Chen, Guoqin; Wang, Xu; Zhang, Yunhe; Yang, Wenshu; Wu, Gaohui

    2012-07-01

    The interface of carbon-fiber-reinforced aluminum matrix (Cf/Al) composites fabricated by the pressure infiltration method with different Mg contents (0, 3.2, 4.5, 6.5, and 8.5 wt pct) was observed by transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM). The Gibbs free energy of Al4C3 and Al3Mg2 was calculated by an extended Miedema model and a Wilson equation. The effect of Mg on the critical nuclear size of Al4C3 was discussed also. The size and number of Al4C3 decreased and transformed from needle-like to blocky with Mg content, and no Al4C3 but blocky β phase (Al3Mg2) was observed at the C-Al interface in the Cf/Al-8.5Mg composite. Increased Mg content in the Al matrix would increase the Gibbs free energy of Al4C3 but decrease that of the Al3Mg2 phase. The critical value of the Mg content, above which the formation of Al3Mg2 would be easier than Al4C3, was 8.8 wt pct when the C activity was 0.0013, which agreed well with the TEM observation. The critical nucleation size of Al4C3 ( {t_{{{{Al}}4 {{C}}3 }}^{*} } ) increased slowly within a low Mg content (less than 8.5 wt pct) and then abruptly after that, indicating the formation of Al4C3 is inhibited significantly in thermodynamic environments. The calculated t_{{{{Al}}4 {{C}}3 }}^{*} in the Cf/Al-6.5Mg composite was 26.3 nm, which was consistent with the HRTEM observation (24 nm).

  20. Effective site-energy model: A thermodynamic approach applied to size-mismatched alloys

    NASA Astrophysics Data System (ADS)

    Berthier, F.; Creuze, J.; Legrand, B.

    2017-06-01

    We present a novel energetic model that takes into account atomistic relaxations to describe the thermodynamic properties of AcB1 -c binary alloys. It requires the calculation of the energies on each site of a random solid solution after relaxation as a function of both the local composition and the nominal concentration. These site energies are obtained by molecular static simulations using N -body interatomic potentials derived from the second-moment approximation (SMA) of the tight-binding scheme. This new model allows us to determine the effective pair interactions (EPIs) that drive the short-range order (SRO) and to analyze the relative role of the EPIs' contribution to the mixing enthalpy, with respect to the contribution due to the lattice mismatch between the constituents. We apply this formalism to Au-Ni and Ag-Cu alloys, both of them tending to phase separate in the bulk and exhibiting a large size mismatch. Rigid-lattice Monte Carlo (MC) simulations lead to phase diagrams that are in good agreement with both those obtained by off-lattice SMA-MC simulations and the experimental ones. While the phase diagrams of Au-Ni and Ag-Cu alloys are very similar, we show that phase separation is mainly driven by the elastic contribution for Au-Ni and by the EPIs' contribution for Ag-Cu. Furthermore, for Au-Ni, the analysis of the SRO shows an inversion between the tendency to order and the tendency to phase separate as a function of the concentration.

  1. 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.

  2. 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…

  3. 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…

  4. 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…

  5. 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…

  6. 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

  7. 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

  8. Influence of non-local thermodynamic equilibrium and Zeeman effects on magnetic equilibrium reconstruction using spectral motional Stark effect diagnostic.

    PubMed

    Reimer, R; Marchuk, O; Geiger, B; Mc Carthy, P J; Dunne, M; Hobirk, J; Wolf, R

    2017-08-01

    The Motional Stark Effect (MSE) diagnostic is a well established technique to infer the local internal magnetic field in fusion plasmas. In this paper, the existing forward model which describes the MSE data is extended by the Zeeman effect, fine-structure, and relativistic corrections in the interpretation of the MSE spectra for different experimental conditions at the tokamak ASDEX Upgrade. The contribution of the non-Local Thermodynamic Equilibrium (non-LTE) populations among the magnetic sub-levels and the Zeeman effect on the derived plasma parameters is different. The obtained pitch angle is changed by 3°…4° and by 0.5°…1° including the non-LTE and the Zeeman effects into the standard statistical MSE model. The total correction is about 4°. Moreover, the variation of the magnetic field strength is significantly changed by 2.2% due to the Zeeman effect only. While the data on the derived pitch angle still could not be tested against the other diagnostics, the results from an equilibrium reconstruction solver confirm the obtained values for magnetic field strength.

  9. Influence of non-local thermodynamic equilibrium and Zeeman effects on magnetic equilibrium reconstruction using spectral motional Stark effect diagnostic

    NASA Astrophysics Data System (ADS)

    Reimer, R.; Marchuk, O.; Geiger, B.; Mc Carthy, P. J.; Dunne, M.; Hobirk, J.; Wolf, R.; ASDEX Upgrade Team

    2017-08-01

    The Motional Stark Effect (MSE) diagnostic is a well established technique to infer the local internal magnetic field in fusion plasmas. In this paper, the existing forward model which describes the MSE data is extended by the Zeeman effect, fine-structure, and relativistic corrections in the interpretation of the MSE spectra for different experimental conditions at the tokamak ASDEX Upgrade. The contribution of the non-Local Thermodynamic Equilibrium (non-LTE) populations among the magnetic sub-levels and the Zeeman effect on the derived plasma parameters is different. The obtained pitch angle is changed by 3 ° … 4 ° and by 0 . 5 ° … 1 ° including the non-LTE and the Zeeman effects into the standard statistical MSE model. The total correction is about 4°. Moreover, the variation of the magnetic field strength is significantly changed by 2.2% due to the Zeeman effect only. While the data on the derived pitch angle still could not be tested against the other diagnostics, the results from an equilibrium reconstruction solver confirm the obtained values for magnetic field strength.

  10. Rotary thermodynamic apparatus and method

    SciTech Connect

    Kantor, F. W.

    1985-06-25

    A rotary inertial thermodynamic absorptive system which can be used as a gas-driven heat pump, a heat-flow-driven gas pump, or, in combination, a heat splitter for moving low-grade heat energy from a lower temperature source to a higher temperature heat sink. In one embodiment, an absorptive type rotary inertial thermodynamic device employs overspill/underspill barriers in its absorption and desorption chambers to achieve counterflow heat exchange therebetween and to ensure effective control of thermodynamic impedance.

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

    NASA Astrophysics Data System (ADS)

    Sade, Ziv; Halevy, Itay

    2017-10-01

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

  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. 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.

  14. 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.

  15. 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.

  16. Computational Studies of Pressure, Temperature, and Surface Effects on the Structure and Thermodynamics of Confined Water

    NASA Astrophysics Data System (ADS)

    Giovambattista, N.; Rossky, P. J.; Debenedetti, P. G.

    2012-05-01

    The behavior of water confined on nanometer length scales is important in a diverse set of technical and scientific contexts, ranging from the performance of fuel cells and biological molecular machines to the design of self-assembling nanoscale materials. Here, we review recent insights into the structure and thermodynamics of confined water that have been elucidated primarily by computer simulation studies. We emphasize investigations in which interfacial chemistry and molecular topography are varied systematically and in which a wide range of thermodynamic conditions of temperature and pressure are explored. We consider homogeneous interfaces ranging from the simplest hard wall to chemically realistic, but structurally ideal, hydrophobic and hydrophilic surfaces, and the continuous scale of surface polarity is investigated. Features associated with interface heterogeneities arising from chemical patterning or from the natural characteristics of protein surfaces are discussed. Finally, we provide our thoughts on important directions for further studies.

  17. Large-n approach to thermodynamic Casimir effects in slabs with free surfaces.

    PubMed

    Diehl, H W; Grüneberg, Daniel; Hasenbusch, Martin; Hucht, Alfred; Rutkevich, Sergei B; Schmidt, Felix M

    2014-06-01

    The classical n-vector ϕ{4} model with O(n) symmetrical Hamiltonian H is considered in a ∞{2}×L slab geometry bounded by a pair of parallel free surface planes at separation L. Standard quadratic boundary terms implying Robin boundary conditions are included in H. The temperature-dependent scaling functions of the excess free energy and the thermodynamic Casimir force are computed in the large-n limit for temperatures T at, above, and below the bulk critical temperature T_{c}. Their n=∞ limits can be expressed exactly in terms of the spectrum and eigenfunctions of a self-consistent one-dimensional Schrödinger equation. This equation is solved by numerical means for two distinct discretized versions of the model: in the first ("model A"), only the coordinate z across the slab is discretized and the integrations over momenta conjugate to the lateral coordinates are regularized dimensionally; in the second ("model B"), a simple cubic lattice with periodic boundary conditions along the lateral directions is used. Renormalization-group ideas are invoked to show that, in addition to corrections to scaling ∝L{-1}, anomalous ones ∝L{-1}lnL should occur. They can be considerably decreased by taking an appropriate g→∞ (T_{c}→∞) limit of the ϕ{4} interaction constant g. Depending on the model A or B, they can be absorbed completely or to a large extent in an effective thickness L_{eff}=L+δL. Excellent data collapses and consistent high-precision results for both models are obtained. The approach to the low-temperature Goldstone values of the scaling functions is shown to involve logarithmic anomalies. The scaling functions exhibit all qualitative features seen in experiments on the thinning of wetting layers of {4}He and Monte Carlo simulations of XY models, including a pronounced minimum of the Casimir force below T_{c}. The results are in conformity with various analytically known exact properties of the scaling functions.

  18. 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

  19. Obtaining effective pair potentials in colloidal monolayers using a thermodynamically consistent inversion scheme.

    PubMed

    Law, A D; Buzza, D M A

    2010-05-18

    The structure and stability of colloidal monolayers depends crucially on the effective pair interaction potential u(r) between colloidal particles. In this study, we construct a novel method for extracting u(r) from the two-dimensional (2D) radial distribution function g(r) of dense colloidal monolayers. The method is based on the Ornstein-Zernike relation and the HMSA closure first proposed by Zerah and Hansen (Zerah, G.; Hansen, J.-P. Self-consistent integral equations for fluid pair distribution functions: Another attempt. J. Chem. Phys. 1986, 84(4), 2336-2343). The HMSA closure contains a single fitting parameter which is determined by requiring thermodynamic consistency between the virial and compressibility equations of state. The accuracy of the HMSA inversion scheme is compared to a 2D predictor corrector scheme based on hard-disk fluids (HDPC) previously proposed by us (Law, A. D.; Buzza, D. M. A. Determination of interaction potentials of colloidal monolayers from the inversion of pair correlation functions: A two-dimensional predictor-corrector method. J. Chem. Phys. 2009, 131, 094704) and the conventional "one-step" inversion methods of HNC and Percus-Yevick (PY). The accuracy of all these schemes is tested against Monte Carlo simulation data for g(r) from monolayers interacting via a range of commonly encountered potentials, including both purely repulsive potentials and potentials containing an attractive well. For all the potentials studied, we find that the accuracy of the HMSA and HDPC schemes is superior to HNC and PY, especially as we go to higher densities. The HDPC and HMSA schemes are particularly accurate for hard-core and soft-core fluids, respectively, at high density and are therefore complementary to each other. Finally, we find that, even in the presence of experimentally realistic levels of noise in the input g(r) data, both HMSA and HDPC schemes are able to faithfully extract the salient features of the underlying interaction

  20. 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

  1. Large-n approach to thermodynamic Casimir effects in slabs with free surfaces

    NASA Astrophysics Data System (ADS)

    Diehl, H. W.; Grüneberg, Daniel; Hasenbusch, Martin; Hucht, Alfred; Rutkevich, Sergei B.; Schmidt, Felix M.

    2014-06-01

    The classical n-vector ϕ4 model with O (n) symmetrical Hamiltonian H is considered in a ∞2×L slab geometry bounded by a pair of parallel free surface planes at separation L. Standard quadratic boundary terms implying Robin boundary conditions are included in H. The temperature-dependent scaling functions of the excess free energy and the thermodynamic Casimir force are computed in the large-n limit for temperatures T at, above, and below the bulk critical temperature Tc. Their n =∞ limits can be expressed exactly in terms of the spectrum and eigenfunctions of a self-consistent one-dimensional Schrödinger equation. This equation is solved by numerical means for two distinct discretized versions of the model: in the first ("model A"), only the coordinate z across the slab is discretized and the integrations over momenta conjugate to the lateral coordinates are regularized dimensionally; in the second ("model B"), a simple cubic lattice with periodic boundary conditions along the lateral directions is used. Renormalization-group ideas are invoked to show that, in addition to corrections to scaling ∝L-1, anomalous ones ∝L-1lnL should occur. They can be considerably decreased by taking an appropriate g →∞ (Tc→∞) limit of the ϕ4 interaction constant g. Depending on the model A or B, they can be absorbed completely or to a large extent in an effective thickness Leff=L+δL. Excellent data collapses and consistent high-precision results for both models are obtained. The approach to the low-temperature Goldstone values of the scaling functions is shown to involve logarithmic anomalies. The scaling functions exhibit all qualitative features seen in experiments on the thinning of wetting layers of 4He and Monte Carlo simulations of XY models, including a pronounced minimum of the Casimir force below Tc. The results are in conformity with various analytically known exact properties of the scaling functions.

  2. 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.

  3. EFFECTS OF LASER RADIATION ON MATTER. LASER PLASMA: Temporal and thermodynamic characteristics of plasma formation

    NASA Astrophysics Data System (ADS)

    Ignatavichyus, M. V.; Kazakyavichyus, É.; Orshevski, G.; Danyunas, V.

    1991-11-01

    An investigation was made of plasma formation accompanying the interaction with aluminum, iron, and VK-6 alloy targets of nanosecond radiation from a YAG:Nd3+ laser (Emax = 50 mJ, τ = 3-8 ns). The duration of the plasma formation process depended weakly on the laser radiation parameters [the power density was varied in the range 1-3 GW/cm2, the pulse rise time in the range 2-8 ns, or the rate of rise of the power density in the range (1-8) × 108 W · cm - 2 · ns -1]. A study was made of the establishment of a local thermodynamic equilibrium in a plasma jet excited by radiation from nanosecond and picosecond (E = 30 mJ, τ = 40 ps) lasers. The maximum of the luminescence from an aluminum plasma excited by picosecond laser radiation was found to correspond to a local thermodynamic equilibrium. A local thermodynamic equilibrium could be absent in the case of excitation by nanosecond laser radiation.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. Phosphorus Control in DRI-EAF Steelmaking: Thermodynamics, Effect of Alumina, and Process Modeling

    NASA Astrophysics Data System (ADS)

    Tayeb, Mohammed A.

    improve. Alumina becomes less acidic acting as a diluting agent and probably forming [AlO6 9-]-octahedra according to which alumina is hypothesized to behave amphoterically. While understanding the equilibrium and kinetics of the phosphorus reaction is important in order to improve the ability to remove phosphorus from the melt, practical use of this understanding in industry is limited. Modeling the phosphorus reaction in steelmaking, however, would result in a better and easier use of conceptual understanding by operators and engineers in plants. This work describes dynamic process models for phosphorus and sulfur reactions when using DRI, scrap, and pig iron in EAF steelmaking. The present models are based on the assumption that thermodynamic equilibrium is locally established at the steel-slag interface, the bulk liquid steel and slag remain homogeneous throughout the reaction, and the rate is predominantly controlled by the mass transfer of phosphorus in the metal and slag boundary layers. The models, which consist of a series of rate and mass balance equations, were converted into a Python code and are capable of predicting trajectories of steel and slag phosphorus and sulfur levels as well as slag chemistry and slag liquid and solid phases. The effect of operating variables on the final phosphorus and sulfur contents, for instance the effect of DRI and pig iron P and S concentrations, oxygen use, temperature, melting rates, and flux addition were tested. The results imply that dephosphorization could be improved by maintaining lower bath temperatures for period of time. Additionally, dephosphorization and desulfurization were improved by higher flux addition.

  9. On the thermodynamic origin of the initial radiation energy density in warm inflation

    NASA Astrophysics Data System (ADS)

    Gim, Yongwan; Kim, Wontae

    2016-11-01

    In warm inflation scenarios, radiation always exists, so that the radiation energy density is also assumed to be finite when inflation starts. To find out the origin of the non-vanishing initial radiation energy density, we revisit thermodynamic analysis for a warm inflation model and then derive an effective Stefan-Boltzmann law which is commensurate with the temperature-dependent effective potential by taking into account the non-vanishing trace of the total energy-momentum tensors. The effective Stefan-Boltzmann law shows that the zero energy density for radiation at the Grand Unification epoch increases until the inflation starts and it becomes eventually finite at the initial stage of warm inflation. By using the above effective Stefan-Boltzmann law, we also study the cosmological scalar perturbation, and obtain the sufficient radiation energy density in order for GUT baryogenesis at the end of inflation.

  10. Direct allowance for the effects of thermodynamic nonideality in the quantitative characterization of protein self-association by osmometry.

    PubMed

    Wills, Peter R; Winzor, Donald J

    2009-12-01

    A procedure is described for the direct analysis of osmotic pressure data for reversibly dimerizing proteins that makes allowance for effects of thermodynamic nonideality on the statistical-mechanical basis of the potential-of-mean-force between molecules. Detailed consideration is also given to calculation of the magnitudes of the required virial coefficients. After illustration of the approach with analysis of simulated osmotic pressure data, the method is used to obtain dimerization constants from published osmotic pressure data for soybean proteinase inhibitor, hemoglobin and alpha-chymotrypsin.

  11. Isentropic calculation for thermodynamic properties of polarized liquid 3He by considering the effect of spin-dependent correlation function

    NASA Astrophysics Data System (ADS)

    Bordbar, G. H.; Hosseini, S.; Poostforush, A.

    2017-05-01

    Correlations in quantum fluids such as liquid 3He continue to be of high interest to scientists. Based on this prospect, the present work is devoted to study the effects of spin-spin correlation function on the thermodynamic properties of polarized liquid 3He such as pressure, velocity of sound, adiabatic index and adiabatic compressibility along different isentropic paths, using the Lennard-Jones potential and employing the variational approach based on cluster expansion of the energy functional. The inclusion of this correlation improves our previous calculations and leads to good agreements with experimental results.

  12. 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.

  13. 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

  14. Thermodynamics "beyond" local equilibrium

    NASA Astrophysics Data System (ADS)

    Vilar, Jose; Rubi, Miguel

    2002-03-01

    Nonequilibrium thermodynamics has shown its applicability in a wide variety of different situations pertaining to fields such as physics, chemistry, biology, and engineering. As successful as it is, however, its current formulation considers only systems close to equilibrium, those satisfying the so-called local equilibrium hypothesis. Here we show that diffusion processes that occur far away from equilibrium can be viewed as at local equilibrium in a space that includes all the relevant variables in addition to the spatial coordinate. In this way, nonequilibrium thermodynamics can be used and the difficulties and ambiguities associated with the lack of a thermodynamic description disappear. We analyze explicitly the inertial effects in diffusion and outline how the main ideas can be applied to other situations. [J.M.G. Vilar and J.M. Rubi, Proc. Natl. Acad. Sci. USA 98, 11081-11084 (2001)].

  15. 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.

  16. 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.

  17. Effect of guanine to inosine substitution on stability of canonical DNA and RNA duplexes: molecular dynamics thermodynamics integration study.

    PubMed

    Krepl, Miroslav; Otyepka, Michal; Banáš, Pavel; Šponer, Jiří

    2013-02-14

    Guanine to inosine (G → I) substitution has often been used to study various properties of nucleic acids. Inosine differs from guanine only by loss of the N2 amino group, while both bases have similar electrostatic potentials. Therefore, G → I substitution appears to be optimally suited to probe structural and thermodynamics effects of single H-bonds and atomic groups. However, recent experiments have revealed substantial difference in free energy impact of G → I substitution in the context of B-DNA and A-RNA canonical helices, suggesting that the free energy changes reflect context-dependent balance of energy contributions rather than intrinsic strength of a single H-bond. In the present study, we complement the experiments by free energy computations using thermodynamics integration method based on extended explicit solvent molecular dynamics simulations. The computations successfully reproduce the basic qualitative difference in free energy impact of G → I substitution in B-DNA and A-RNA helices although the magnitude of the effect is somewhat underestimated. The computations, however, do not reproduce the salt dependence of the free energy changes. We tentatively suggest that the different effect of G → I substitution in A-RNA and B-DNA may be related to different topologies of these helices, which affect the electrostatic interactions between the base pairs and the negatively charged backbone. Limitations of the computations are briefly discussed.

  18. 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.

  19. 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.

  20. 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.

  1. 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)

  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. Revisiting the effective medium approximation in all-dielectric subwavelength multilayers: Breakdown and rebuilding

    NASA Astrophysics Data System (ADS)

    Lei, Xinrui; Mao, Lei; Lu, Yonghua; Wang, Pei

    2017-07-01

    Here, we present a comprehensive analysis of the effective medium approximation (EMA) breakdown in all-dielectric deep-subwavelength multilayers made of alternating layers by means of the transfer matrix method. We demonstrated that the approximation is invalid at the vicinity of the effective medium's critical angle for total internal reflection and obtained an analytical criterion for the breakdown of the EMA, which depends on the layer thickness, the incident angle, and the permittivity difference between the alternate layers. We rebuilt the EMA by adding higher-order correction onto the traditional effective permittivity. Furthermore, we found that the EMA breakdown that arises from the boundary effect cannot be repaired in the traditional homogenization strategy with only one layer of effective medium. By adding an artificial matched layer after the conventional effective layer, the boundary effect breakdown was neatly removed.

  4. Thermodynamic analysis and effect of crystallinity for silicon monoxide negative electrode for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Yasuda, Kouji; Kashitani, Yusuke; Kizaki, Shingo; Takeshita, Kohki; Fujita, Takehisa; Shimosaki, Shinji

    2016-10-01

    The electrochemical behavior of SiO negative electrodes for lithium ion batteries is thermodynamically and experimentally investigated. The analysis of the reaction pathway and the calculation of the reaction potentials during the Li insertion/extraction reactions are carried out by the construction of the ternary phase diagram for the Li-Si-O system. In the initial reaction of Li insertion, metallic Si and lithium silicates are formed above 0.37 V vs. Li/Li+ as a conversion reaction of the SiO negative electrode. Further Li insertion produces Li-Si alloys as reversible reaction phases. The decomposition of the Li4SiO4 phase begins before the formation of the Li-Si alloy is completed. The measured electrode behavior of the SiO negative electrode basically agrees with the thermodynamic calculations, especially at a low reaction rate; deviations can be ascribed to kinetic factors and electrode resistance. The values of over 1898 mA h g-1 and 71.0% were obtained for the discharge capacity and the coulombic efficiency, respectively. Furthermore, the overvoltage for an amorphous SiO electrode was smaller than that for a disproportionated SiO electrode into Si and SiO2 phases.

  5. 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.

  6. 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.

  7. 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

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. The face inversion effect in non-human primates revisited - an investigation in chimpanzees (Pan troglodytes)

    PubMed Central

    Dahl, Christoph D.; Rasch, Malte J.; Tomonaga, Masaki; Adachi, Ikuma

    2013-01-01

    Faces presented upside-down are harder to recognize than presented right-side up, an effect known as the face inversion effect. With inversion the perceptual processing of the spatial relationship among facial parts is disrupted. Previous literature indicates a face inversion effect in chimpanzees toward familiar and conspecific faces. Although these results are not inconsistent with findings from humans they have some controversy in their methodology. Here, we employed a delayed matching-to-sample task to test captive chimpanzees on discriminating chimpanzee and human faces. Their performances were deteriorated by inversion. More importantly, the discrimination deterioration was systematically different between the two age groups of chimpanzee participants, i.e. young chimpanzees showed a stronger inversion effect for chimpanzee than for human faces, while old chimpanzees showed a stronger inversion effect for human than for chimpanzee faces. We conclude that the face inversion effect in chimpanzees is modulated by the level of expertise of face processing. PMID:23978930

  13. 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

  14. Effects of scandium composition on the structural, electronic, and thermodynamic properties of SCxY1-x metallic alloys

    NASA Astrophysics Data System (ADS)

    López-Pérez, W.; Castro-Diago, P.; Ramírez-Montes, L.; González-García, A.; González-Hernández, R.

    2016-02-01

    The aim of this work is to analyse the compositional dependence of the structural, electronic and thermodynamic properties of ? alloys. Density functional calculations have been carried out to reveal compositional dependence of the structural, electronic and thermodynamic properties of ? alloys. The lattice constants of the binary compounds are in fairly good agreement with the available experimental data. The variation of calculated lattice constant with scandium concentration is almost linear, and shows a slight deviation from Vegard's law. The effect of scandium composition on bulk modulus gives nonlinear dependence on concentration x. A small deviation of the bulk modulus from linear concentration dependence was observed. The metallic nature of binary precursor compounds ScP and YP was confirmed. Our findings indicate that the ? alloys are metallic for ? 0.25, 0.5, 0.75. The calculated excess mixing enthalpy is positive over the entire scandium composition range. The positive mixing enthalpies indicate meta-stability of the ? alloys at high temperatures. The effect of temperature on the volume, bulk modulus, Debye temperature and the heat capacity for ? alloys were analysed using the quasi-harmonic Debye model. Results show that the heat capacity is slightly sensitive to composition as temperature increases.

  15. Strong effects of thermodynamic ice-shelf/ocean interactions in a globalsea-icea-ocean isopycnal model

    NASA Astrophysics Data System (ADS)

    Sergienko, O. V.; Harrison, M.; Hallberg, R.

    2016-02-01

    Melting/refreezing of ice shelves have strong impacts both on ice shelves (through modification of their shape) and on the ocean circulation ( through modification of their water masses). Representation of ice-shelf/ocean interaction in the global ocean circulation models continues to be challenging. Using a high-resolution (1/8 deg) global isopycnal ocean model, MOM6, and a sea-ice model, SIS, we investigate the effects of thermodynamic coupling of the Antarctic ice shelves on the various aspects of ocean circulation. Such high (3-8 km) horizontal spatial resolution allows for detailed resolution of the sub-ice-shelf cavity circulations. The computed ice-shelves melt rates are in very good agreement with observationally derived melt rate estimates. The spatial distributions of simulated melting/freezing rates indicate enhanced melting in the vicinity of the grounding line and very strong melting at the ice-shelves front. Results of our simulations show strong effects of sub-ice-shelf melt water on circulation of the Southern Ocean. We also find that simulations accounting for the thermodynamic coupling of the Antarctic ice shelves produce consistently thicker sea ice compared to the uncoupled simulations.

  16. Effects of Monofunctional Adducts of Platinum(II) Complexes on Thermodynamic Stability and Energetics of DNA Duplexes

    PubMed Central

    Bursova, Vendula; Kasparkova, Jana; Hofr, Ctirad; Brabec, Viktor

    2005-01-01

    Effects of adducts of [PtCl(NH3)3]Cl or chlorodiethylenetriamineplatinum(II) on DNA stability were studied with emphasis on thermodynamic origins of that stability. Oligodeoxyribonucleotide duplexes (15-bp) containing the single, site-specific monofunctional adduct at G-residues of the central sequences TGT/ACA or 5′-AGT/5′-ACT were prepared and analyzed by differential scanning calorimetry, temperature-dependent ultraviolet absorption and circular dichroism. The unfolding of the platinated duplexes was accompanied by relatively small unfavorable free energy terms. This destabilization was enthalpic in origin. On the other hand, a relatively large reduction of melting temperature (Tm) was observed as a consequence of the monofunctional adduct in the TGT sequence, whereas Tm due to the adduct in the AGT sequence was reduced only slightly. We also examined the efficiency of the mammalian nucleotide excision repair system to remove from DNA the monofunctional adducts and found that these lesions were not recognized by this repair system. Thus, rather thermodynamic than thermal characterization of DNA adducts of monofunctional platinum compounds is a property implicated in the modulation of downstream effects such as protein recognition and repair. PMID:15574710

  17. 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.

  18. 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.

  19. 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.

  20. 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…

  1. 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…

  2. 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…

  3. 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…

  4. 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

  5. Large-deviation principles, stochastic effective actions, path entropies, and the structure and meaning of thermodynamic descriptions

    NASA Astrophysics Data System (ADS)

    Smith, Eric

    2011-04-01

    The meaning of thermodynamic descriptions is found in large-deviations scaling (Ellis 1985 Entropy, Large Deviations, and Statistical Mechanics (New York: Springer); Touchette 2009 Phys. Rep. 478 1-69) of the probabilities for fluctuations of averaged quantities. The central function expressing large-deviations scaling is the entropy, which is the basis both for fluctuation theorems and for characterizing the thermodynamic interactions of systems. Freidlin-Wentzell theory (Freidlin and Wentzell 1998 Random Perturbations in Dynamical Systems 2nd edn (New York: Springer)) provides a quite general formulation of large-deviations scaling for non-equilibrium stochastic processes, through a remarkable representation in terms of a Hamiltonian dynamical system. A number of related methods now exist to construct the Freidlin-Wentzell Hamiltonian for many kinds of stochastic processes; one method due to Doi (1976 J. Phys. A: Math. Gen. 9 1465-78 1976 J. Phys. A: Math. Gen. 9 1479) and Peliti (1985 J. Physique 46 1469; 1986 J. Phys. A: Math. Gen. 19 L365, appropriate to integer counting statistics, is widely used in reaction-diffusion theory. Using these tools together with a path-entropy method due to Jaynes (1980 Annu. Rev. Phys. Chem. 31 579-601), this review shows how to construct entropy functions that both express large-deviations scaling of fluctuations, and describe system-environment interactions, for discrete stochastic processes either at or away from equilibrium. A collection of variational methods familiar within quantum field theory, but less commonly applied to the Doi-Peliti construction, is used to define a 'stochastic effective action', which is the large-deviations rate function for arbitrary non-equilibrium paths. We show how common principles of entropy maximization, applied to different ensembles of states or of histories, lead to different entropy functions and different sets of thermodynamic state variables. Yet the relations among all these levels of

  6. 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

  7. 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

  8. 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.

  9. The demise of short-term memory revisited: empirical and computational investigations of recency effects.

    PubMed

    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 from the short-term store. In this article, evidence is reviewed showing that recency effects in the short and long terms have different properties, and it is suggested that 2 memory components are needed to account for the recency effects: an episodic contextual system with changing context and an activation-based short-term memory buffer that drives the encoding of item-context associations. A neurocomputational model based on these 2 components is shown to account for previously observed dissociations and to make novel predictions, which are confirmed in a set of experiments.

  10. 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.

  11. 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)

  12. 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)

  13. 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.

  14. 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.

  15. 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

  16. 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

  17. Revisiting the cost-effectiveness of universal cervical length screening: importance of progesterone efficacy.

    PubMed

    Jain, Siddharth; Kilgore, Meredith; Edwards, Rodney K; Owen, John

    2016-07-01

    Preterm birth (PTB) is a significant cause of neonatal morbidity and mortality. Studies have shown that vaginal progesterone therapy for women diagnosed with shortened cervical length can reduce the risk of PTB. However, published cost-effectiveness analyses of vaginal progesterone for short cervix have not considered an appropriate range of clinically important parameters. To evaluate the cost-effectiveness of universal cervical length screening in women without a history of spontaneous PTB, assuming that all women with shortened cervical length receive progesterone to reduce the likelihood of PTB. A decision analysis model was developed to compare universal screening and no-screening strategies. The primary outcome was the cost-effectiveness ratio of both the strategies, defined as the estimated patient cost per quality-adjusted life-year (QALY) realized by the children. One-way sensitivity analyses were performed by varying progesterone efficacy to prevent PTB. A probabilistic sensitivity analysis was performed to address uncertainties in model parameter estimates. In our base-case analysis, assuming that progesterone reduces the likelihood of PTB by 11%, the incremental cost-effectiveness ratio for screening was $158,000/QALY. Sensitivity analyses show that these results are highly sensitive to the presumed efficacy of progesterone to prevent PTB. In a 1-way sensitivity analysis, screening results in cost-saving if progesterone can reduce PTB by 36%. Additionally, for screening to be cost-effective at WTP=$60,000 in three clinical scenarios, progesterone therapy has to reduce PTB by 60%, 34% and 93%. Screening is never cost-saving in the worst-case scenario or when serial ultrasounds are employed, but could be cost-saving with a two-day hospitalization only if progesterone were 64% effective. Cervical length screening and treatment with progesterone is a not a dominant, cost-effective strategy unless progesterone is more effective than has been suggested by

  18. 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.

  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. 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

  1. Models and mechanisms of Hofmeister effects in electrolyte solutions, and colloid and protein systems revisited.

    PubMed

    Salis, Andrea; Ninham, Barry W

    2014-11-07

    Specific effects of electrolytes have posed a challenge since the 1880's. The pioneering work was that of Franz Hofmeister who studied specific salt induced protein precipitation. These effects are the rule rather the exception and are ubiquitous in chemistry and biology. Conventional electrostatic theories (Debye-Hückel, DLVO, etc.) cannot explain such effects. Over the past decades it has been recognised that additional quantum mechanical dispersion forces with associated hydration effects acting on ions are missing from theory. In parallel Collins has proposed a phenomenological set of rules (the law of matching water affinities, LMWA) which explain and bring to order the order of ion-ion and ion-surface site interactions at a qualitative level. The two approaches appear to conflict. Although the need for inclusion of quantum dispersion forces in one form or another is not questioned, the modelling has often been misleading and inappropriate. It does not properly describe the chemical nature (kosmotropic/chaotropic or hard/soft) of the interacting species. The success of the LMWA rules lies in the fact that they do. Here we point to the way that the two apparently opposing approaches might be reconciled. Notwithstanding, there are more challenges, which deal with the effect of dissolved gas and its connection to 'hydrophobic' interactions, the problem of water at different temperatures and 'water structure' in the presence of solutes. They take us to another dimension that requires the rebuilding of theoretical foundations.

  2. 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.

  3. 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.

  4. Concreteness effects revisited: the influence of dynamic visual noise on memory for concrete and abstract words.

    PubMed

    Parker, Andrew; Dagnall, Neil

    2009-05-01

    Two experiments are presented that investigate the effects of dynamic visual noise (DVN) on memory for concrete and abstract words. Memory for concrete words is typically superior to that of abstract words and is referred to as the concreteness effect. DVN is a procedure that has been demonstrated to interfere selectively with visual working memory and the generation of images from long-term memory. It was reasoned that if concreteness effects arise because of the ability of the latter to activate visual representations, then DVN should selectively impair memory for concrete words. Experiment 1 found DVN to selectively reduce free recall of concrete words. Experiment 2 investigated recognition memory and found DVN to reduce memory accuracy and remember responses, while increasing know responses to concrete words.

  5. 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. Copyright © 2015 The Authors. Published by Elsevier B.V. All rights reserved.

  6. 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.

  7. Anomeric effect revisited: Perspective from information-theoretic approach in density functional reactivity theory

    NASA Astrophysics Data System (ADS)

    Zhou, Xiayu; Yu, Donghai; Rong, Chunying; Lu, Tian; Liu, Shubin

    2017-09-01

    In this work, we apply the quantities from the information-theoretic approach in density functional reactivity theory to examine the origin and nature of the anomeric effect, which is the preference of heteroatomic substituents within the cyclohexane ring to be in the axial orientation rather than the sterically less hindered equatorial position. Using α-D-glucopyranose as an example, we confirmed its complex stereoelectronic origin. With Shannon entropy, Fisher information, GBP entropy, information gain, Onicescu information energy, and relative Renyi entropy, we are able to accurately account for the axial-equatorial energy difference in general, with the anomeric effect included as a special case.

  8. The effect of iron on montmorillonite stability. (I) Background and thermodynamic considerations

    NASA Astrophysics Data System (ADS)

    Wilson, James; Savage, David; Cuadros, Javier; Shibata, Masahiro; Ragnarsdottir, K. Vala

    2006-01-01

    It is envisaged that high-level nuclear waste (HLW) will be disposed of in underground repositories. Many proposed repository designs include steel waste canisters and bentonite backfill. Natural analogues and experimental data indicate that the montmorillonite component of the backfill could react with steel corrosion products to produce non-swelling Fe-rich phyllosilicates such as chamosite, berthierine, or Fe-rich smectite. In K-bearing systems, the alteration of montmorillonite to illite/glauconite could also be envisaged. If montmorillonite were altered to non-swelling minerals, the swelling capacity and self-healing properties of the bentonite backfill could be reduced, thereby diminishing backfill performance. The main aim of this paper was to investigate Fe-rich phyllosilicate mineral stability at the canister-backfill interface using thermodynamic modelling. Estimates of thermodynamic properties were made for Fe-rich clay minerals in order to construct approximate phase-relations for end-member/simplified mineral compositions in logarithmic activity space. Logarithmic activity diagrams (for the system Al 2O 3-FeO-Fe 2O 3-MgO-Na 2O-SiO 2-H 2O) suggest that if pore waters are supersaturated with respect to magnetite in HLW repositories, Fe(II)-rich saponite is the most likely montmorillonite alteration product (if f values are significantly lower than magnetite-hematite equilibrium). Therefore, the alteration of montmorillonite may not be detrimental to nuclear waste repositories that include Fe, as long as the swelling behaviour of the Fe-rich smectite produced is maintained. If f exceeds magnetite-hematite equilibrium, and solutions are saturated with respect to magnetite in HLW repositories, berthierine is likely to be more stable than smectite minerals. The alteration of montmorillonite to berthierine could be detrimental to the performance of HLW repositories.

  9. 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…

  10. The Element Effect Revisited: Factors Determining Leaving Group Ability in Activated Nucleophilic Aromatic Substitution Reactions

    PubMed Central

    Senger, Nicholas A.; Bo, Bo; Cheng, Qian; Keeffe, James R.; Gronert, Scott; Wu, Weiming

    2012-01-01

    The “element effect” in nucleophilic aromatic substitution reactions (SNAr) is characterized by the leaving group order, F > NO2 > Cl ≈ Br > I, in activated aryl halides. Multiple causes for this result have been proposed. Experimental evidence shows that the element effect order in the reaction of piperidine with 2,4-dinitrophenyl halides in methanol is governed by the differences in enthalpies of activation. Computational studies of the reaction of piperidine and dimethylamine with the same aryl halides using the polarizable continuum model (PCM) for solvation indicate that polar, polarizability, solvation, and negative hyperconjugative effects are all of some importance in producing the element effect in methanol. In addition, a reversal of polarity of the C–X bond from reactant to transition state in the case of ArCl and ArBr compared to ArF also contributes to their difference in reactivity. The polarity reversal, and hyperconjugative influences have received little or no attention in the past. Nor has differential solvation of the different transition states been strongly emphasized. An anionic nucleophile, thiolate, gives very early transition states and negative activation enthalpies with activated aryl halides. The element effect is not established for these reactions. We suggest that the leaving group order in the gas phase will be dependent on the exact combination of nucleophile, leaving group, and substrate framework. The geometry of the SNAr transition state permits useful, qualitative conceptual distinctions to be made between this reaction and other modes of nucleophilic attack. PMID:23057717

  11. 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…

  12. 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…

  13. 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…

  14. 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'…

  15. 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…

  16. 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…

  17. 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'…

  18. 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…

  19. 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…

  20. 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…

  1. 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…

  2. 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…

  3. 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…

  4. 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.

  5. 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…

  6. 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,…

  7. 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…

  8. 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…

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. The efficiency of a group-specific mandated benefit revisited: the effect of infertility mandates.

    PubMed

    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 unaffected, but their total labor input decreases. Workers do not value infertility mandates at cost, and so will not take wage cuts in exchange, leading employers to decrease their demand for this affected and identifiable group. Differences in the empirical effects of mandates found in the literature are explained by a model including variations in the elasticity of demand, moral hazard, ability to identify a group, and adverse selection.

  15. Revisiting the thermal effect on shock wave propagation in weakly ionized plasmas

    SciTech Connect

    Zhou, Qianhong Dong, Zhiwei; Yang, Wei

    2016-07-15

    Many researchers have investigated shock propagation in weakly ionized plasmas and observed the following anomalous effects: shock acceleration, shock recovery, shock weakening, shock spreading, and splitting. It was generally accepted that the thermal effect can explain most of the experimental results. However, little attention was paid to the shock recovery. In this paper, the shock wave propagation in weakly ionized plasmas is studied by fluid simulation. It is found that the shock acceleration, weakening, and splitting appear after it enters the plasma (thermal) region. The shock splits into two parts right after it leaves the thermal region. The distance between the splitted shocks keeps decreasing until they recover to one. This paper can explain a whole set of features of the shock wave propagation in weakly ionized plasmas. It is also found that both the shock curvature and the splitting present the same photoacoustic deflection (PAD) signals, so they cannot be distinguished by the PAD experiments.

  16. 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.

  17. 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.

  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. An old experiment revisited: the Doppler effect in a ripple tank

    NASA Astrophysics Data System (ADS)

    D'Anna, M.; Corridoni, T.

    2016-07-01

    Studying waves on a water surface, in this paper we present an approach to the Doppler effect that enables students to not only perceive it qualitatively, but also to construct experimentally the well known quantitative relations, which are usually introduced in a rather formal way. The interpretation of these relations is then obtained and discussed exploiting space-time diagrams, whose role is emphasized especially in view of extending this approach to phenomena involving light.

  20. Revisiting the iris effect of tropical cirrus clouds with TRMM and A-Train satellite data

    NASA Astrophysics Data System (ADS)

    Choi, Yong-Sang; Kim, WonMoo; Yeh, Sang-Wook; Masunaga, Hirohiko; Kwon, Min-Jae; Jo, Hyun-Su; Huang, Lei

    2017-06-01

    Just as the iris of human eye controls the light influx (iris effect), tropical anvil cirrus clouds may regulate the Earth's surface warming by controlling outgoing longwave radiation. This study examines this possible effect with monthly satellite observations such as Tropical Rainfall Measuring Mission (TRMM) precipitation, Moderate Resolution Imaging Spectroradiometer cirrus fraction, and Clouds and the Earth's Radiant Energy System top-of-the-atmosphere radiative fluxes averaged over different tropical domains from March 2000 to October 2014. To confirm that high-level cirrus is relevant to this study, Cloud-Aerosol Lidar with Orthogonal Polarization high cloud observations were also analyzed from June 2006 to December 2015. Our analysis revealed that the increase in sea surface temperature in the tropical western Pacific tends to concentrate convective cloud systems. This concentration effect very likely induces the significant reduction of both stratiform rain rate and cirrus fraction, without appreciable change in the convective rain rate. This reduction of stratiform rain rate and cirrus fraction cannot be found over its subregion or the tropical eastern Pacific, where the concentration effect of anvil cirrus is weak. Consistently, over the tropical western Pacific, the higher ratio of convective rain rate to total rain rate (i.e., precipitation efficiency) significantly correlates with warmer sea surface temperature and lower cirrus fraction. The reduced cirrus eventually increased outgoing longwave radiation to a greater degree than absorbed solar radiation. Finally, the negative relationship between precipitation efficiency and cirrus fraction tends to correspond to a low global equilibrium climate sensitivity in the models in the Coupled Model Intercomparison Project Phase 5. This suggests that tropical anvil cirrus clouds exert a negative climate feedback in strong association with precipitation efficiency.

  1. Revisiting the effectiveness of interventions to decrease surgical site infections in colorectal surgery: A Bayesian perspective.

    PubMed

    Phatak, Uma R; Pedroza, Claudia; Millas, Stefanos G; Chang, George J; Lally, Kevin P; Kao, Lillian S

    2012-08-01

    To evaluate the evidence for interventions to decrease surgical site infections (SSIs) in colorectal operations using Bayesian meta-analysis. Interventions other than appropriate administration of prophylactic antibiotics to prevent SSIs have not been adopted widely, in part because of lack of recommendations for these interventions based on traditional meta-analyses. Bayesian methods can provide probabilities of specific thresholds of benefit, which may be more useful in guiding clinical decision making. We hypothesized that Bayesian meta-analytic methods would complement the interpretation of traditional analyses regarding the effectiveness of interventions to decrease SSIs. We conducted a systematic search of the Cochrane database for reviews of interventions to decrease SSIs after colorectal surgery other than prophylactic antibiotics. Traditional and Bayesian meta-analyses were performed using RevMan (Nordic Cochrane Center, Copenhagen, Denmark) and WinBUGS (MRC Biostatistics Unit, Cambridge, UK). Bayesian posterior probabilities of any benefit, defined as a relative risk of <1, were calculated using skeptical, neutral, and enthusiastic prior probabilities. Probabilities were also calculated that interventions decreased SSIs by ≥10%, and ≥20% using neutral prior probability distributions. A total of 9 Cochrane reviews met the search criteria. Using traditional meta-analysis methods, only laparoscopic colorectal surgery resulted in a significant reduction in SSIs and a recommendation for use of the intervention. Using Bayesian analysis, several interventions that did not result in "significant" decreases in SSIs using traditional analytic methods had a >85% probability of benefit. Also, nonuse of 2 interventions (mechanical bowel preparation and adhesive drapes) had a high probability of decreasing SSIs compared with their use. Bayesian probabilities and traditional point estimates of treatment effect yield similar information in terms of potential

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. Effects of dark energy on geodesics and thermodynamics of the Schwarzschild-de Sitter space-time

    NASA Astrophysics Data System (ADS)

    Ghaderi, K.; Malakolkalami, B.

    2017-09-01

    The effects of quintessence on geodesics and thermodynamics of the Schwarzschild-de Sitter black hole are studied and the results are compared with the case without the presence of quintessence. We show that the presence of quintessence increases the entropy and heat capacity of the Schwarzschild-de Sitter black hole and decreases the mass and temperature of this black hole. In particular, we focused on types of orbits and we found that the coordinate time, circular orbits, period of the circular orbits and the angle of deflection of light for this black hole increase in quintessence field while the quintessence decreases the effective potential, force on the massless particle, Lyapunov exponent λ and closest approach.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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

  12. 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.

  13. 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.

  14. Natural thermodynamics

    NASA Astrophysics Data System (ADS)

    Annila, Arto

    2016-02-01

    The principle of increasing entropy is derived from statistical physics of open systems assuming that quanta of actions, as undividable basic build blocks, embody everything. According to this tenet, all systems evolve from one state to another either by acquiring quanta from their surroundings or by discarding quanta to the surroundings in order to attain energetic balance in least time. These natural processes result in ubiquitous scale-free patterns: skewed distributions that accumulate in a sigmoid manner and hence span log-log scales mostly as straight lines. Moreover, the equation for least-time motions reveals that evolution is by nature a non-deterministic process. Although the obtained insight in thermodynamics from the notion of quanta in motion yields nothing new, it accentuates that contemporary comprehension is impaired when modeling evolution as a computable process by imposing conservation of energy and thereby ignoring that quantum of actions are the carriers of energy from the system to its surroundings.

  15. 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".

  16. 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.

  17. 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

  18. Revisiting the Effectiveness of Standard Antidepressants in Bipolar Disorder: Are Monoamine Oxidase Inhibitors Superior?

    PubMed Central

    Mallinger, Alan G.; Frank, Ellen; Thase, Michael E.; Barwell, Michelle M.; DiazGranados, Nancy; Luckenbaugh, David A.; Kupfer, David J.

    2011-01-01

    Objective The role of antidepressants in bipolar disorder is controversial, and the comparative effectiveness of specific drugs is insufficiently studied. We report here a comparison of monoamine oxidase inhibitors (MAOI) with the serotonin reuptake inhibitor paroxetine (PAROX). Experimental Design We conducted a retrospective analysis of data from a larger study, using the first antidepressant trial administered either after entry (n = 46) or after a recurrent episode during study participation (n = 6). Twenty two patients were treated with PAROX and 30 with MAOI. Durable recovery was determined from Hamilton depression and Young mania scores, based on published criteria. Principal Observations PAROX treatment led to durable recovery in 27% of patients, a result very similar to the 24% recovery rate found in a recent STEP-BD trial. In contrast, patients treated with MAOI had a 53% durable recovery rate. Survival analysis showed a significantly faster recovery with MAOI (χ2 = 4.77, p = 0.029). Among subjects who were able to complete an adequate treatment trial of at least four weeks duration, durable recovery was attained in a significantly greater proportion of those treated with MAOI (16 of 23, 70%) as compared to PAROX (6 of 18, 33%)(Fisher's Exact Test, p = 0.023). Conclusions In these patients with bipolar depression, the antidepressant effectiveness of PAROX was unacceptably low, but rates of recovery with MAOI were significantly higher. PMID:19629023

  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. 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

  1. 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.

  2. 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

  3. 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.

  4. Revisiting Hispanic adolescents' resilience to the effects of parental problem drinking and life stress.

    PubMed

    Barrera, Manuel; Hageman, Devon N; Gonzales, Nancy A

    2004-09-01

    Two previous studies found that life stress and parental alcoholism were not as highly related to distress for Hispanic adolescents as they were for European American adolescents (M. Barrera Jr., S. A. Li, and L. Chassin, 1993, 1995). Those findings could be interpreted as evidence of Hispanic youths' resilience, but limitations of the stress measure and the homogeneity of the Hispanic sample threatened this interpretation. The present study improved on those previous studies by using a new measure of uncontrollable stressors and a more heterogeneous Mexican American sample. Participants in this study were 175 Mexican American and 59 European American adolescents and their parents. Unlike the previous studies, results did not show that Mexican American adolescents were more resilient to parental problem drinking or life stress than were European American adolescents. Overall, life stress was related to adolescents', mothers', and fathers' reports of adolescents' psychological distress above and beyond the effects of ethnicity and socioeconomic factors.

  5. 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

  6. 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.

  7. Healing and the invention of metaphor: the effectiveness of symbols revisited.

    PubMed

    Kirmayer, L J

    1993-06-01

    In this essay, I argue that a theory of meaning adequate to account for the effectiveness of symbolic healing and psychotherapy requires some variant of the three concepts of myth, metaphor and archetype. Myth stands for the overarching narrative structures of the self produced and lent authority by cultural tradition. Archetype stands not for performed ideas or images, but for the bodily-given in meaning. Metaphor occupies an intermediate realm, linking narrative and bodily-given experience through imaginative constructions and enactments that allow movement in sensory-affective quality space. This pluralistic perspective itself constitutes a middle-ground between constructivist and realist approaches to meaning that can integrate causal and interpretive models of symbolic healing.

  8. 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.

  9. 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

  10. Prioritization and the elusive effect on welfare - a Norwegian health care reform revisited.

    PubMed

    Aakvik, Arild; Holmås, Tor Helge; Kjerstad, Egil

    2015-03-01

    The Faster Return to Work (FRW) scheme that Norwegian authorities implemented in 2007 is an example of a policy that builds on the human capital approach. The main idea behind the scheme is that long waiting times for hospital treatment lead to unnecessarily long periods of absence from work. To achieve a reduction in average sickness absence duration, the allocation of FRW funds and new treatment capacity is exclusively aimed at people on sick leave. Many countries have allocated funds to reduce waiting times for hospital treatment and research shows that more resources allocated to the hospital sector can reduce waiting times. Our results support this as the FRW scheme significantly reduces waiting times. However, on average the reduction in waiting times is not transformed into an equally large reduction in the sickness absence period. We find significant difference in the effects of FRW on length of sick leave between surgical and non-surgical patients though. The duration of sick leave for FRW patients undergoing surgical treatment is approximately 14 days shorter than for surgical patients on the regular waiting list. We find no significant effect of the scheme on length of sick leave for non-surgical patients. In sum, our welfare analysis indicates that prioritization of the kind that the FRW scheme represents is not as straightforward as one would expect. The FRW scheme costs more than it contributes in reduced productivity loss. We base our analyses on several different econometric methods using register data on approximately 13,500 individuals over the period 2007-2008. Copyright © 2015 Elsevier Ltd. All rights reserved.

  11. 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.

  12. Thermodynamic Constraints Improve Metabolic Networks.

    PubMed

    Krumholz, Elias W; Libourel, Igor G L

    2017-08-08

    In pursuit of establishing a realistic metabolic phenotypic space, the reversibility of reactions is thermodynamically constrained in modern metabolic networks. The reversibility constraints follow from heuristic thermodynamic poise approximations that take anticipated cellular metabolite concentration ranges into account. Because constraints reduce the feasible space, draft metabolic network reconstructions may need more extensive reconciliation, and a larger number of genes may become essential. Notwithstanding ubiquitous application, the effect of reversibility constraints on the predictive capabilities of metabolic networks has not been investigated in detail. Instead, work has focused on the implementation and validation of the thermodynamic poise calculation itself. With the advance of fast linear programming-based network reconciliation, the effects of reversibility constraints on network reconciliation and gene essentiality predictions have become feasible and are the subject of this study. Networks with thermodynamically informed reversibility constraints outperformed gene essentiality predictions compared to networks that were constrained with randomly shuffled constraints. Unconstrained networks predicted gene essentiality as accurately as thermodynamically constrained networks, but predicted substantially fewer essential genes. Networks that were reconciled with sequence similarity data and strongly enforced reversibility constraints outperformed all other networks. We conclude that metabolic network analysis confirmed the validity of the thermodynamic constraints, and that thermodynamic poise information is actionable during network reconciliation. Copyright © 2017 Biophysical Society. Published by Elsevier Inc. All rights reserved.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. The foreperiod effect revisited: conditioning as a basis for nonspecific preparation.

    PubMed

    Los, S A; Knol, D L; Boers, R M

    2001-01-01

    The foreperiod (FP) is the interval between a warning stimulus and the imperative stimulus. It is a classical finding that both the duration and the intertrial variability of FP considerably affects response time. These effects are invariably attributed to the participant's state of nonspecific preparation at the moment the imperative stimulus is presented. In this article, we examined a proposal by Los, S. A. (1996) [On the origin of mixing costs: exploring information processing in pure and mixed blocks of trials. Acta Psychologica, 94, 145-188] that the real-time development of nonspecific preparation during FP relies on the same principle as trace conditioning. To this end, we adjusted the formal conditioning model developed by Machado, A. (1997) [Learning the temporal dynamics of behavior. Psychological Review, 104 (2), 241-265], and fitted this model to a representative data set we obtained from nine participants. Although the model accounted for only a moderate proportion of the variance, it accurately reproduced several key features of the data. We therefore concluded that the model is a promising first step toward a theory of nonspecific preparation.

  18. 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.

  19. Effective water clearance and tonicity balance: the excretion of water revisited.

    PubMed

    Mallie, J P; Bichet, D G; Halperin, M L

    1997-02-01

    To demonstrate (1) that hyponatremia is usually due to an inappropriately low rate of excretion of electrolyte-free water and (2) that the measure "effective water clearance" (EWC) provides better information about renal defence of the body tonicity than does the classic measure free-water clearance, and to provide the rationale for calculating a "tonicity balance," which involves using water and sodium plus potassium intakes and their renal excretion to reveal the basis for changes in body tonicity. Prospective study. Four normal subjects with no conditions affecting excretion, 10 patients with advanced congestive heart failure (CHF) and 5 patients with the syndrome of inappropriate antidiuretic hormone secretion (SIADH). Normals and patients were administered a standard water load (20 mL per kg of body weight) during 45 minutes, and blood and urine samples were taken before, during and after the load was given. Urine and blood sodium and potassium concentrations, osmolar clearance, free-water clearance, electrolyte clearance and EWC. The water load was excreted rapidly by normals, more slowly by patients with CHF, and not at all by patients with SIADH. The EWC was positive in normals and those with CHF, but negative in those with SIADH. In patients with CHF, the EWC, but not the free-water clearance, helped explain why hyponatremia was corrected after the water load was given. In subjects with abnormal water excretion, the EWC provides the physiologic explanation for the renal role in variations in natremia. The authors propose a bedside evaluation of renal water and electrolyte handling that takes into consideration the role of urinary potassium in body tonicity. Changes in body tonicity can be explained by a "tonicity balance," a calculation in which the source and the net balance of sodium, potassium and water are considered.

  20. The Angelina effect revisited: Exploring a media-related impact on public awareness.

    PubMed

    Lebo, Patricia Beatrice; Quehenberger, Franz; Kamolz, Lars-Peter; Lumenta, David Benjamin

    2015-11-15

    In 2013, Angelina Jolie's double mastectomy and publication of her personal treatment choice for BRCA1 positivity generated considerable media attention. To the authors' knowledge, the current study is the first prospective survey conducted among the general public to measure a quantifiable media-related effect on public awareness. The authors analyzed the changes in the general public's awareness of reconstructive options in breast cancer among 2 female population-matched cohorts aged 18 to 65 years (1000 participants in each cohort) before (March 2013; poll 1) and after (June 2013; poll 2) the announcement of Ms. Jolie's mastectomy in May 2013. There was an observed increase in public awareness: significantly more women from poll 2 were aware of reconstructive breast surgery being possible after breast cancer-related mastectomy, notably with regard to autologous tissue and single-stage reconstructions. Approximately 20% of the women in poll 2 (205 women) indicated that media coverage regarding Ms. Jolie affected their interest in breast cancer. A question that was exclusive to poll 2 revealed a preference for autologous (66.2%) versus implant-based (8.2%) reconstructions, with the remainder indicating no preference (25.6%). None of the stratification variables were found to be associated with the above findings. To the best of the authors' knowledge, this is the first prospective study to demonstrate a statistically significant impact of a celebrity announcement on public awareness regarding breast cancer treatment. The results underscore the importance of a media-related impact for professionals in the health care sector, which can serve as a tipping point for raising awareness and improving knowledge concerning a specific disease among the general public. © 2015 American Cancer Society.

  1. 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

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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

  8. Revisiting Curriculum Potential

    ERIC Educational Resources Information Center

    Deng, Zongyi

    2011-01-01

    This article analyzes the notion of curriculum potential by revisiting the ideas of Miriam Ben-Peretz and Joseph Schwab. Invoking the German "Didaktik" tradition and by way of a curriculum-making framework, the paper argues that interpreting curriculum materials for curriculum potential requires a careful analysis and unpacking of the meanings and…

  9. 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…

  10. 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…

  11. 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…

  12. Swedish Successful Schools Revisited

    ERIC Educational Resources Information Center

    Hoog, Jonas; Johansson, Olof; Olofsson, Anders

    2009-01-01

    Purpose: The purpose of this paper is to describe the results of a follow-up study of two Swedish schools in which, five years previously, the principals had been successful leaders. Had this success been maintained? Design/methodology/approach: Two schools were revisited to enable the authors to interview principals and teachers as well as…

  13. 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.

  14. 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…

  15. 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 ...

  16. 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…

  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. 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 ...

  19. Revisiting Teachers as Learners

    ERIC Educational Resources Information Center

    Thomson, Liz

    2008-01-01

    This article revisits the concept of teachers as learners within the context of radical changes that have taken place within the education system in England over the past 25 years. The concept of "professional courage" is discussed and examined in relation to questions and issues raised by Paulo Freire in a series of letters to teachers…

  20. 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…

  1. 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.

  2. 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. Copyright © 2015 Elsevier B.V. All rights reserved.

  3. Pressure effect on the mechanical, electronic and thermodynamic properties of Ba2Bi3: First-principle calculations

    NASA Astrophysics Data System (ADS)

    Cao, Jin-Jin; Gou, Xiao-Fan

    2017-05-01

    The newly discovered Ba2Bi3 phase has attracted attentions in search of new superconductors, mainly because of the layered structure with two-dimensional superconducting Bi planes intercalated by Ba atoms. To clearly reveal what features the layered structure of the Ba2Bi3 phase correlates with, especially under pressure, we have systematically investigated the structural, mechanical, electronic and thermodynamic properties under the equivalent hydrostatic pressures up to 14 GPa by means of first-principle calculations with the Local Density Approximation (LDA) and Generalized Gradient Approximation (GGA) approaches. The results indicate that the pressure effect on the crystal structure is performed as a compression of the unit-cell volume, mainly along the c-axis. Specifically for the mechanical related properties, the elastic constants and polycrystalline elastic moduli monotonically increase with the pressure. The calculated ductile factors show that the Ba2Bi3 lies in between the brittle and ductile border line at 0 GPa and the pressure makes the ductility enhancement. Besides, the anisotropic properties of the Ba2Bi3 under various pressures are discussed. The electronic energy band structure and density of states under pressure are analyzed. Moreover, the pressure and temperature dependence of the thermodynamic properties through the quasi-harmonic Debye model, together with the pressure dependence of the Debye temperature calculated from elastic constants has been obtained. The calculated results of the variation of the Debye temperature and total density of states at Fermi level show that the pressure can lead to the superconducting transition temperature (Tc) of the Ba2Bi3 decreasing.

  4. 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.

  5. 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…

  6. 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…

  7. 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.

  8. 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

  9. 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.

  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. 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

  12. Thermodynamics of protein-protein interactions of cMyc, Max, and Mad: effect of polyions on protein dimerization.

    PubMed

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

    2006-02-21

    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 DeltaH degrees and DeltaS degrees from the temperature dependence of K(d) 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.

  13. Thermodynamic Investigation of the Effect of Interface Curvature on the Solid-Liquid Equilibrium and Eutectic Point of Binary Mixtures.

    PubMed

    Liu, Fanghui; Zargarzadeh, Leila; Chung, Hyun-Joong; Elliott, Janet A W

    2017-09-29

    Thermodynamic phase behavior is affected by curved interfaces in micro- and nanoscale systems. For example, capillary freezing point depression is associated with the pressure difference between the solid and liquid phases caused by interface curvature. In this study, the thermal, mechanical, and chemical equilibrium conditions are derived for binary solid-liquid equilibrium with a curved solid-liquid interface due to confinement in a capillary. This derivation shows the equivalence of the most general forms of the Gibbs-Thomson and Ostwald-Freundlich equations. As an example, the effect of curvature on solid-liquid equilibrium is explained quantitatively for the water/glycerol system. Considering the effect of a curved solid-liquid interface, a complete solid-liquid phase diagram is developed over a range of concentrations for the water/glycerol system (including the freezing of pure water or precipitation of pure glycerol depending on the concentration of the solution). This phase diagram is compared with the traditional phase diagram in which the assumption of a flat solid-liquid interface is made. We show the extent to which nanoscale interface curvature can affect the composition-dependent freezing and precipitating processes, as well as the change in the eutectic point temperature and concentration with interface curvature. Understanding the effect of curvature on solid-liquid equilibrium in nanoscale capillaries has applications in the food industry, soil science, cryobiology, nanoporous materials, and various nanoscience fields.

  14. 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

  15. Thermodynamics of barnase unfolding.

    PubMed

    Griko, Y V; Makhatadze, G I; Privalov, P L; Hartley, R W

    1994-04-01

    The thermodynamics of barnase denaturation has been studied calorimetrically over a broad range of temperature and pH. It is shown that in acidic solutions the heat denaturation of barnase is well approximated by a 2-state transition. The heat denaturation of barnase proceeds with a significant increase of heat capacity, which determines the temperature dependencies of the enthalpy and entropy of its denaturation. The partial specific heat capacity of denatured barnase is very close to that expected for the completely unfolded protein. The specific denaturation enthalpy value extrapolated to 130 degrees C is also close to the value expected for the full unfolding. Therefore, the calorimetrically determined thermodynamic characteristics of barnase denaturation can be considered as characteristics of its complete unfolding and can be correlated with structural features--the number of hydrogen bonds, extent of van der Waals contacts, and the surface areas of polar and nonpolar groups. Using this information and thermodynamic information on transfer of protein groups into water, the contribution of various factors to the stabilization of the native structure of barnase has been estimated. The main contributors to the stabilization of the native state of barnase appear to be intramolecular hydrogen bonds. The contributions of van der Waals interactions between nonpolar groups and those of hydration effects of these groups are not as large if considered separately, but the combination of these 2 factors, known as hydrophobic interactions, is of the same order of magnitude as the contribution of hydrogen bonding.

  16. 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.

  17. 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.

  18. 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.

  19. Versatility of Cooperative Transcriptional Activation: A Thermodynamical Modeling Analysis for Greater-Than-Additive and Less-Than-Additive Effects

    PubMed Central

    Frank, Till D.; Carmody, Aimée M.; Kholodenko, Boris N.

    2012-01-01

    We derive a statistical model of transcriptional activation using equilibrium thermodynamics of chemical reactions. We examine to what extent this statistical model predicts synergy effects of cooperative activation of gene expression. We determine parameter domains in which greater-than-additive and less-than-additive effects are predicted for cooperative regulation by two activators. We show that the statistical approach can be used to identify different causes of synergistic greater-than-additive effects: nonlinearities of the thermostatistical transcriptional machinery and three-body interactions between RNA polymerase and two activators. In particular, our model-based analysis suggests that at low transcription factor concentrations cooperative activation cannot yield synergistic greater-than-additive effects, i.e., DNA transcription can only exhibit less-than-additive effects. Accordingly, transcriptional activity turns from synergistic greater-than-additive responses at relatively high transcription factor concentrations into less-than-additive responses at relatively low concentrations. In addition, two types of re-entrant phenomena are predicted. First, our analysis predicts that under particular circumstances transcriptional activity will feature a sequence of less-than-additive, greater-than-additive, and eventually less-than-additive effects when for fixed activator concentrations the regulatory impact of activators on the binding of RNA polymerase to the promoter increases from weak, to moderate, to strong. Second, for appropriate promoter conditions when activator concentrations are increased then the aforementioned re-entrant sequence of less-than-additive, greater-than-additive, and less-than-additive effects is predicted as well. Finally, our model-based analysis suggests that even for weak activators that individually induce only negligible increases in promoter activity, promoter activity can exhibit greater-than-additive responses when

  20. Revisiting the carboxylic acid dimers in aqueous solution: interplay of hydrogen bonding, hydrophobic interactions, and entropy.

    PubMed

    Chen, Jianhan; Brooks, Charles L; Scheraga, Harold A

    2008-01-17

    Carboxylic acid dimers are useful model systems for understanding the interplay of hydrogen bonding, hydrophobic effects, and entropy in self-association and assembly. Through extensive sampling with a classical force field and careful free energy analysis, it is demonstrated that both hydrogen bonding and hydrophobic interactions are indeed important for dimerization of carboxylic acids (except formic acid). The dimers are only weakly ordered, and the degree of ordering increases with stronger hydrophobic interactions between longer alkyl chains. Comparison of calculated and experimental dimerization constants reveals a systematic tendency for excessive self-aggregation in current classical force fields. Qualitative and quantitative information on the thermodynamics of hydrogen bonding and hydrophobic interactions derived from these simulations is in excellent agreement with existing results from experiment and theory. These results provide a verification from first principles of previous estimations based on two statistical mechanical hydrophobic theories. We also revisit and clarify the fundamental statistical thermodynamics formalism for calculating absolute binding constants, external entropy, and solvation entropy changes upon association from detailed free energy simulations. This analysis is believed to be useful for a wide range of applications including computational studies of protein-ligand and protein-protein binding.

  1. 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.

  2. 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.

  3. 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.

  4. Measuring Thermodynamic Length

    SciTech Connect

    Crooks, Gavin E

    2007-09-07

    Thermodynamic length is a metric distance between equilibrium thermodynamic states. Among other interesting properties, this metric asymptotically bounds the dissipation induced by a finite time transformation of a thermodynamic system. It is also connected to the Jensen-Shannon divergence, Fisher information, and Rao's entropy differential metric. Therefore, thermodynamic length is of central interestin understanding matter out of equilibrium. In this Letter, we will consider how to denethermodynamic length for a small system described by equilibrium statistical mechanics and how to measure thermodynamic length within a computer simulation. Surprisingly, Bennett's classic acceptance ratio method for measuring free energy differences also measures thermodynamic length.

  5. 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…

  6. 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…

  7. Mass Spectrometric Immunoassay Revisited

    PubMed Central

    Nelson, Randall W.; Borges, Chad R.

    2013-01-01

    The progressive understanding and improvement of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS), realized over the years through the considerable efforts of Dr. Marvin Vestal, have made possible numerous comparable efforts involving its application in the biological sciences. Here we revisit the concepts behind one such analytical approach, Mass Spectrometric Immunoassay, which is designed to selectively detect and quantify proteins present in biological milieu. PMID:21953037

  8. 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

  9. 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.

  10. 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…

  11. 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…

  12. Thermodynamic Studies for Drug Design and Screening

    PubMed Central

    Garbett, Nichola C.; Chaires, Jonathan B.

    2012-01-01

    Introduction A key part of drug design and development is the optimization of molecular interactions between an engineered drug candidate and its binding target. Thermodynamic characterization provides information about the balance of energetic forces driving binding interactions and is essential for understanding and optimizing molecular interactions. Areas covered This review discusses the information that can be obtained from thermodynamic measurements and how this can be applied to the drug development process. Current approaches for the measurement and optimization of thermodynamic parameters are presented, specifically higher throughput and calorimetric methods. Relevant literature for this review was identified in part by bibliographic searches for the period 2004 – 2011 using the Science Citation Index and PUBMED and the keywords listed below. Expert opinion The most effective drug design and development platform comes from an integrated process utilizing all available information from structural, thermodynamic and biological studies. Continuing evolution in our understanding of the energetic basis of molecular interactions and advances in thermodynamic methods for widespread application are essential to realize the goal of thermodynamically-driven drug design. Comprehensive thermodynamic evaluation is vital early in the drug development process to speed drug development towards an optimal energetic interaction profile while retaining good pharmacological properties. Practical thermodynamic approaches, such as enthalpic optimization, thermodynamic optimization plots and the enthalpic efficiency index, have now matured to provide proven utility in design process. Improved throughput in calorimetric methods remains essential for even greater integration of thermodynamics into drug design. PMID:22458502

  13. The "Wallpaper Effect" Revisited: Divergent Findings on the Effects of Intergroup Contact on Attitudes in Diverse Versus Nondiverse Contexts.

    PubMed

    Schmid, Katharina; Wölfer, Ralf; Swart, Herman; Christ, Oliver; Al Ramiah, Ananthi; Vertovec, Steven; Hewstone, Miles

    2017-09-01

    This article reexamines the so-called "wallpaper effect" of intergroup contact, which contends that for minority group members living in areas more densely populated by majority group members, intergroup contact fails to reduce prejudice. We tested this claim in five studies, using data from five countries, two types of contexts, a range of measures, and involving different minority versus majority groups. Using multilevel cross-level interaction models, we considered whether effects of contact on outgroup attitudes were moderated by relative outgroup size. Results failed to replicate the previously reported findings, revealing, by and large, nonsignificant cross-level moderation effects; instead, we witnessed consistent positive contact effects on attitudes. Findings are discussed against the backdrop of recent research on the consequences of diversity, as well as context-based considerations regarding minority versus majority constellations. We also discuss some exceptions to our findings that emerged for some respondent groups and contexts across the five studies.

  14. 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

  15. 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.

  16. Acute Kidney Injury: Controversies Revisited

    PubMed Central

    Yong, Kenneth; Dogra, Gursharan; Boudville, Neil; Pinder, Mary; Lim, Wai

    2011-01-01

    This paper addresses the epidemiology of AKI specifically in relation to recent changes in AKI classification and revisits the controversies regarding the timing of initiation of dialysis and the use of peritoneal dialysis as a renal replacement therapy for AKI. In summary, the new RIFLE/AKIN classifications of AKI have facilitated more uniform diagnosis of AKI and clinically significant risk stratification. Regardless, the issue of timing of dialysis initiation still remains unanswered and warrants further examination. Furthermore, peritoneal dialysis as a treatment modality for AKI remains underutilised in spite of potential beneficial effects. Future research should be directed at identifying early reliable biomarkers of AKI, which in conjunction with RIFLE/AKIN classifications of AKI could facilitate well-designed large randomised controlled trials of early versus late initiation of dialysis in AKI. In addition, further studies of peritoneal dialysis in AKI addressing dialysis dose and associated complications are required for this therapy to be accepted more widely by clinicians. PMID:21660314

  17. 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.

  18. 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.

  19. 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.

  20. 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.