Application of the compensated Arrhenius formalism to explain the dielectric constant dependence of rates for Menschutkin reactions.

PubMed

Petrowsky, Matt; Glatzhofer, Daniel T; Frech, Roger

2013-11-21

The dependence of the reaction rate on solvent dielectric constant is examined for the reaction of trihexylamine with 1-bromohexane in a series of 2-ketones over the temperature range 25-80 °C. The rate constant data are analyzed using the compensated Arrhenius formalism (CAF), where the rate constant assumes an Arrhenius-like equation that also contains a dielectric constant dependence in the exponential prefactor. The CAF activation energies are substantially higher than those obtained using the simple Arrhenius equation. A master curve of the data is observed by plotting the prefactors against the solvent dielectric constant. The master curve shows that the reaction rate has a weak dependence on dielectric constant for values approximately less than 10 and increases more rapidly for dielectric constant values greater than 10.

Triprotic acid-base microequilibria and pharmacokinetic sequelae of cetirizine.

PubMed

Marosi, Attila; Kovács, Zsuzsanna; Béni, Szabolcs; Kökösi, József; Noszál, Béla

2009-06-28

(1)H NMR-pH titrations of cetirizine, the widely used antihistamine and four related compounds were carried out and the related 11 macroscopic protonation constants were determined. The interactivity parameter between the two piperazine amine groups was obtained from two symmetric piperazine derivatives. Combining these two types of datasets, all the 12 microconstants and derived tautomeric constants of cetirizine were calculated. Upon this basis, the conflicting literature data of cetirizine microspeciation were clarified, and the pharmacokinetic absorption-distribution properties could be interpreted. The pH-dependent distribution of the microspecies is provided.

D-(U-11C)glucose uptake and metabolism in the brain of insulin-dependent diabetic subjects

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gutniak, M.; Blomqvist, G.; Widen, L.

1990-05-01

We used D-(U-11C)glucose to evaluate transport and metabolism of glucose in the brain in eight nondiabetic and six insulin-dependent diabetes mellitus (IDDM) subjects. IDDM subjects were treated by continuous subcutaneous insulin infusion. Blood glucose was regulated by a Biostator-controlled glucose infusion during a constant insulin infusion. D-(U-11C)-glucose was injected for positron emission tomography studies during normoglycemia as well as during moderate hypoglycemia (arterial plasma glucose 2.74 +/- 0.14 in nondiabetic and 2.80 +/- 0.26 mmol/l (means +/- SE) in IDDM subjects). Levels of free insulin were constant and similar in both groups. The tracer data were analyzed using a three-compartmentmore » model with a fixed correction for 11CO2 egression. During normoglycemia the influx rate constant (k1) and blood-brain glucose flux did not differ between the two groups. During hypoglycemia k1 increased significantly and similarly in both groups (from 0.061 +/- 0.007 to 0.090 +/- 0.006 in nondiabetic and from 0.061 +/- 0.006 to 0.093 +/- 0.013 ml.g-1.min-1 in IDDM subjects). During normoglycemia the tracer-calculated metabolism of glucose was higher in the whole brain in the nondiabetic than in the diabetic subjects (22.0 +/- 1.9 vs. 15.6 +/- 1.1 mumol.100 g-1.min-1, P less than 0.01). During hypoglycemia tracer-calculated metabolism was decreased by 40% in nondiabetic subjects and by 28% in diabetic subjects. The results indicate that uptake of glucose is normal, but some aspect of glucose metabolism is abnormal in a group of well-controlled IDDM subjects.« less

Temperature and size-dependent Hamaker constants for metal nanoparticles

NASA Astrophysics Data System (ADS)

Jiang, K.; Pinchuk, P.

2016-08-01

Theoretical values of the Hamaker constant have been calculated for metal nanoparticles using Lifshitz theory. The theory describes the Hamaker constant in terms of the permittivity of the interacting bodies. Metal nanoparticles exhibit an internal size effect that alters the dielectric permittivity of the particle when its size falls below the mean free path of the conducting electrons. This size dependence of the permittivity leads to size-dependence of the Hamaker constant for metal nanoparticles. Additionally, the electron damping and the plasma frequency used to model the permittivity of the particle exhibit temperature-dependence, which lead to temperature dependence of the Hamaker constant. In this work, both the size and temperature dependence for gold, silver, copper, and aluminum nanoparticles is demonstrated. The results of this study might be of interest for studying the colloidal stability of nanoparticles in solution.

Temperature and size-dependent Hamaker constants for metal nanoparticles.

PubMed

Jiang, K; Pinchuk, P

2016-08-26

Theoretical values of the Hamaker constant have been calculated for metal nanoparticles using Lifshitz theory. The theory describes the Hamaker constant in terms of the permittivity of the interacting bodies. Metal nanoparticles exhibit an internal size effect that alters the dielectric permittivity of the particle when its size falls below the mean free path of the conducting electrons. This size dependence of the permittivity leads to size-dependence of the Hamaker constant for metal nanoparticles. Additionally, the electron damping and the plasma frequency used to model the permittivity of the particle exhibit temperature-dependence, which lead to temperature dependence of the Hamaker constant. In this work, both the size and temperature dependence for gold, silver, copper, and aluminum nanoparticles is demonstrated. The results of this study might be of interest for studying the colloidal stability of nanoparticles in solution.

Investigation of ciliary propulsion of Tetrahymena Pyriformis in viscous solution

NASA Astrophysics Data System (ADS)

Jung, Ilyong; Lyubich, Eva; Valles, James

2014-03-01

Recent experiments by our group showed that the ciliated protist Paramecium Caudatumswims with a constant propulsive force in solutions with viscosities 1 < η/ ηw<7 where ηw is the viscosity of water. Measurements of the geometry of its helical swimming trajectory combined with high speed video of the ciliary motion provided insight into this behavior. Using a phenomenological model we found that the body cilia beating frequency decreases while the beating angle remains roughly constant to produce the constant propulsive force dependence on viscosity. In this talk, we present studies of another ciliated protozoa, Tetrahymena Pyriformis to determine whether the behavior of Paramecium is general. Preliminary results indicate that Tetrahymena Pyriformis also swims with a nearly constant propulsive force with increasing viscosity. Investigations similar to those performed on Paramecium are underway and the latest results will be presented. This work was supported by NSF PHY0750360 and at the NHMFL by NSF DMR-0084173

The Dependence of the Spring Constant in the Linear Range on Spring Parameters

ERIC Educational Resources Information Center

Khotimah, Siti Nurul; Viridi, Sparisoma; Widayani; Khairurrijal

2011-01-01

In basic physics laboratories, springs are normally used to determine both spring constants and the Earth's gravitational acceleration. Students generally do not notice that the spring constant is not a universal constant, but depends on the spring parameters. This paper shows and verifies that the spring constant in the linear range is inversely…

MODELING OF METAL BINDING ON HUMIC SUBSTANCES USING THE NIST DATABASE: AN A PRIORI FUNCTIONAL GROUP APPROACH

EPA Science Inventory

Various modeling approaches have been developed for metal binding on humic substances. However, most of these models are still curve-fitting exercises-- the resulting set of parameters such as affinity constants (or the distribution of them) is found to depend on pH, ionic stren...

Vibration-rotation interactions and ring-puckering in 3,3-dimethyl oxetane by microwave spectroscopy

NASA Astrophysics Data System (ADS)

López, Juan C.; Lesarri, Alberto G.; Villamañán, Rosa M.; Alonso, Josél.

1990-06-01

Ring puckering in 3,3-dimethyl oxetane has been investigated using microwave spectroscopy. Microwave spectra of the ground state, the first six ring-puckering excited states, and nine excited states of the methyl groups' deformation vibrations have been observed. The μa electric dipole moment component has been determined as 2.03(3) D from Stark-effect measurements. The vibrational dependence of the rotational constants is consistent with the ring-puckering potential function derived by Duckett et al. ( J. Mol. Spectrosc.69, 159-165 (1978)). Coriolis coupling interactions have been observed and are satisfactorily accounted for with a quartic centrifugal distortion Hamiltonian. The vibrational dependence of the centrifugal distortion constants has been analyzed using the theory developed by Creswell and Mills. In order to reproduce the experimental value of the vibration-rotation interaction parameter, {δμ ab}/{δQ}, a dynamical model allowing the rocking of the CH 3CCH 3 group should be used. The equilibrium ring puckering angle calculated with this model and the ring-puckering potential function is 17.5°.

Photo-dynamics of roseoflavin and riboflavin in aqueous and organic solvents

NASA Astrophysics Data System (ADS)

Zirak, P.; Penzkofer, A.; Mathes, T.; Hegemann, P.

2009-03-01

Roseoflavin (8-dimethylamino-8-demethyl- D-riboflavin) and riboflavin in aqueous and organic solvents are studied by optical absorption spectroscopy, fluorescence spectroscopy, and fluorescence decay kinetics. Solvent polarity dependent absorption shifts are observed. The fluorescence quantum yields are solvent dependent. For roseoflavin the fluorescence decay shows a bi-exponential dependence (ps to sub-ps time constant, and 100 ps to a few ns time constant). The roseoflavin photo-dynamics is explained in terms of fast intra-molecular charge transfer (diabatic electron transfer) from the dimethylamino electron donor group to the pteridin carbonyl electron acceptor followed by intra-molecular charge recombination. The fast fluorescence component is due to direct locally-excited-state emission, and the slow fluorescence component is due to delayed locally-excited-state emission and charge transfer state emission. The fluorescence decay of riboflavin is mono-exponential. The S 1-state potential energy surface is determined by vibronic relaxation and solvation dynamics due to excited-state dipole moment changes (adiabatic optical electron transfer).

Orientation dependence of elastic and piezomagnetic properties in NiFe2O4

NASA Astrophysics Data System (ADS)

Jian, Gang; Xue, Fei; Zhang, Chen; Yan, Chao; Zhao, Ning; Wong, C. P.

2017-11-01

In this paper, the crystal orientation dependence of the elastic and piezomagnetic properties have been calculated for nickel ferrite (NiFe2O4) in three-dimensional space by means of coordinate transformations. The maximum elastic compliances s11‧, s12‧ and piezomagnetic constants q31‧, q33‧ along specific orientations have been determined based on experimental data of NiFe2O4 and original matrices for m3m point group. The piezomagnetic constants q31‧ and q33‧ show highly dependence on crystal orientation compared with elastic compliances s11‧, s12‧, meanwhile permittivity μ33‧ is a constant. The max s11‧ and s12‧ can be obtained along directions [n k l] (n·k = 0, l ≠ 0) and [n k l] (n·k·l = 0), respectively. The max q31‧ and max q33‧ lie along [0 0 1] and [1 1 1] axes, respectively, NiFe2O4||[1 1 1] axis can produce large q31‧ and q33‧ at the same time. The result suggests that by adopting the optimal directions, the elastic and piezomagnetic properties of the devices made from NiFe2O4 can be precisely modulated.

To Evaluate & Compare Retention of Complete Cast Crown in Natural Teeth Using Different Auxiliary Retentive Features with Two Different Crown Heights - An In Vitro Study.

PubMed

Vinaya, Kundapur; Rakshith, Hegde; Prasad D, Krishna; Manoj, Shetty; Sunil, Mankar; Naresh, Shetty

2015-06-01

To evaluate the retention of complete cast crowns in teeth with adequate and inadequate crown height and to evaluate the effects of auxiliary retentive features on retention form complete cast crowns. Sixty freshly extracted human premolars. They were divided into 2 major groups depending upon the height of the teeth after the preparation. Group1 (H1): prepared teeth with constant height of 3.5 mm and Group 2 (H2): prepared teeth with constant height of 2.5 mm. Each group is further subdivided into 3 subgroups, depending upon the retentive features incorporated. First sub group were prepared conventionally, second sub group with proximal grooves and third subgroups with proximal boxes preparation. Castings produced in Nickel chromium alloy were cemented with glass ionomer cement and the cemented castings were subjected to tensional forces required to dislodge each cemented casting from its preparation and used for comparison of retentive quality. The data obtained were statistically analyzed using Oneway ANOVA test. The results showed there was statistically significant difference between adequate (H1) and inadequate (H2) group and increase in retention when there was incorporation of retentive features compared to conventional preparations. Incorporation of retentive grooves was statistically significant compared to retention obtained by boxes. Results also showed there was no statistically significant difference between long conventional and short groove. Complete cast crowns on teeth with adequate crown height exhibited greater retention than with inadequate crown height. Proximal grooves provided greater amount of retention when compared with proximal boxes.

Simple and Double Alfven Waves: Hamiltonian Aspects

NASA Astrophysics Data System (ADS)

Webb, G. M.; Zank, G. P.; Hu, Q.; le Roux, J. A.; Dasgupta, B.

2011-12-01

We discuss the nature of simple and double Alfvén waves. Simple waves depend on a single phase variable \\varphi, but double waves depend on two independent phase variables \\varphi1 and \\varphi2. The phase variables depend on the space and time coordinates x and t. Simple and double Alfvén waves have the same integrals, namely, the entropy, density, magnetic pressure, and group velocity (the sum of the Alfvén and fluid velocities) are constant throughout the flow. We present examples of both simple and double Alfvén waves, and discuss Hamiltonian formulations of the waves.

Representations of the quantum doubles of finite group algebras and spectral parameter dependent solutions of the Yang-Baxter equation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dancer, K. A.; Isac, P. S.; Links, J.

2006-10-15

Quantum doubles of finite group algebras form a class of quasitriangular Hopf algebras that algebraically solve the Yang-Baxter equation. Each representation of the quantum double then gives a matrix solution of the Yang-Baxter equation. Such solutions do not depend on a spectral parameter, and to date there has been little investigation into extending these solutions such that they do depend on a spectral parameter. Here we first explicitly construct the matrix elements of the generators for all irreducible representations of quantum doubles of the dihedral groups D{sub n}. These results may be used to determine constant solutions of the Yang-Baxtermore » equation. We then discuss Baxterization ansaetze to obtain solutions of the Yang-Baxter equation with a spectral parameter and give several examples, including a new 21-vertex model. We also describe this approach in terms of minimal-dimensional representations of the quantum doubles of the alternating group A{sub 4} and the symmetric group S{sub 4}.« less

Interpretation of neutrino-matter interactions at low energies as contraction of gauge group of Electroweak Model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gromov, N. A., E-mail: gromov@dm.komisc.ru

The very weak neutrino-matter interactions are explained with the help of the gauge group contraction of the standard Electroweak Model. The mathematical contraction procedure is connected with the energy dependence of the interaction cross section for neutrinos and corresponds to the limiting case of the Electroweak Model at low energies. Contraction parameter is connected with the universal Fermi constant of weak interactions and neutrino energy as j{sup 2}(s) = {radical}(G{sub F} s)

Binding constants of membrane-anchored receptors and ligands depend strongly on the nanoscale roughness of membranes.

PubMed

Hu, Jinglei; Lipowsky, Reinhard; Weikl, Thomas R

2013-09-17

Cell adhesion and the adhesion of vesicles to the membranes of cells or organelles are pivotal for immune responses, tissue formation, and cell signaling. The adhesion processes depend sensitively on the binding constant of the membrane-anchored receptor and ligand proteins that mediate adhesion, but this constant is difficult to measure in experiments. We have investigated the binding of membrane-anchored receptor and ligand proteins with molecular dynamics simulations. We find that the binding constant of the anchored proteins strongly decreases with the membrane roughness caused by thermally excited membrane shape fluctuations on nanoscales. We present a theory that explains the roughness dependence of the binding constant for the anchored proteins from membrane confinement and that relates this constant to the binding constant of soluble proteins without membrane anchors. Because the binding constant of soluble proteins is readily accessible in experiments, our results provide a useful route to compute the binding constant of membrane-anchored receptor and ligand proteins.

Corruption: Taking into account the psychological mimicry of officials

NASA Astrophysics Data System (ADS)

Kolesin, Igor; Malafeyev, Oleg; Andreeva, Mariia; Ivanukovich, Georgiy

2017-07-01

A mathematical model of corruption with regard to psychological mimicry in the administrative apparatus with three forms of corruption is constructed. It is assumed that the change of officials forms of corruption is due to situational factors, and anti-corruption laws imply the change of the dominant form. Form's changing is modeled by the system of four differential equations (including groups of corrupt officials), describing the number of groups. The speed of the transition from group to group is expressed through the frequency of meetings. The controlling influence is expressed through the force of anticorruption laws. Two cases are discussed: strictly constant and variable (depending on the scope of one or another form). The equilibrium states that allow to specify the dominant form and investigate its stability, depending on the parameters of the psychological mimicry and rigor of anti-corruption laws are found and discussed.

NMR experiments for the rapid identification of P=O···H-X type hydrogen bonds in nucleic acids.

PubMed

Duchardt-Ferner, Elke; Wöhnert, Jens

2017-10-01

Hydrogen bonds involving the backbone phosphate groups occur with high frequency in functional RNA molecules. They are often found in well-characterized tertiary structural motifs presenting powerful probes for the rapid identification of these motifs for structure elucidation purposes. We have shown recently that stable hydrogen bonds to the phosphate backbone can in principle be detected by relatively simple NMR-experiments, providing the identity of both the donor hydrogen and the acceptor phosphorous within the same experiment (Duchardt-Ferner et al., Angew Chem Int Ed Engl 50:7927-7930, 2011). However, for imino and hydroxyl hydrogen bond donor groups rapidly exchanging with the solvent as well as amino groups broadened by conformational exchange experimental sensitivity is severely hampered by extensive line broadening. Here, we present improved methods for the rapid identification of hydrogen bonds to phosphate groups in nucleic acids by NMR. The introduction of the SOFAST technique into 1 H, 31 P-correlation experiments as well as a BEST-HNP experiment exploiting 3h J N,P rather than 2h J H,P coupling constants enables the rapid and sensitive identification of these hydrogen bonds in RNA. The experiments are applicable for larger RNAs (up to ~ 100-nt), for donor groups influenced by conformational exchange processes such as amino groups and for hydrogen bonds with rather labile hydrogens such as 2'-OH groups as well as for moderate sample concentrations. Interestingly, the size of the through-hydrogen bond scalar coupling constants depends not only on the type of the donor group but also on the structural context. The largest coupling constants were measured for hydrogen bonds involving the imino groups of protonated cytosine nucleotides as donors.

Kinetics of phloretin binding to phosphatidylcholine vesicle membranes

PubMed Central

1980-01-01

The submillisecond kinetics for phloretin binding to unilamellar phosphatidylcholine (PC) vesicles was investigated using the temperature-jump technique. Spectrophotometric studies of the equilibrium binding performed at 328 nm demonstrated that phloretin binds to a single set of independent, equivalent sites on the vesicle with a dissociation constant of 8.0 microM and a lipid/site ratio of 4.0. The temperature of the phloretin-vesicle solution was jumped by 4 degrees C within 4 microseconds producing a monoexponential, concentration-dependent relaxation process with time constants in the 30--200-microseconds time range. An analysis of the concentration dependence of relaxation time constants at pH 7.30 and 24 degrees C yielded a binding rate constant of 2.7 X 10(8) M-1 s-1 and an unbinding constant of 2,900 s-1; approximately 66 percent of total binding sites are exposed at the outer vesicle surface. The value of the binding rate constant and three additional observations suggest that the binding kinetics are diffusion limited. The phloretin analogue, naringenin, which has a diffusion coefficient similar to phloretin yet a dissociation constant equal to 24 microM, bound to PC vesicle with the same rate constant as phloretin did. In addition, the phloretin-PC system was studied in buffers made one to six times more viscous than water by addition of sucrose or glycerol to the differ. The equilibrium affinity for phloretin binding to PC vesicles is independent of viscosity, yet the binding rate constant decreases with the expected dependence (kappa binding alpha 1/viscosity) for diffusion-limited processes. Thus, the binding rate constant is not altered by differences in binding affinity, yet depends upon the diffusion coefficient in buffer. Finally, studies of the pH dependence of the binding rate constant showed a dependence (kappa binding alpha [1 + 10pH-pK]) consistent with the diffusion-limited binding of a weak acid. PMID:7391812

Interactions of poly(amidoamine) dendrimers with human serum albumin: binding constants and mechanisms.

PubMed

Giri, Jyotsnendu; Diallo, Mamadou S; Simpson, André J; Liu, Yi; Goddard, William A; Kumar, Rajeev; Woods, Gwen C

2011-05-24

The interactions of nanomaterials with plasma proteins have a significant impact on their in vivo transport and fate in biological fluids. This article discusses the binding of human serum albumin (HSA) to poly(amidoamine) [PAMAM] dendrimers. We use protein-coated silica particles to measure the HSA binding constants (K(b)) of a homologous series of 19 PAMAM dendrimers in aqueous solutions at physiological pH (7.4) as a function of dendrimer generation, terminal group, and core chemistry. To gain insight into the mechanisms of HSA binding to PAMAM dendrimers, we combined (1)H NMR, saturation transfer difference (STD) NMR, and NMR diffusion ordered spectroscopy (DOSY) of dendrimer-HSA complexes with atomistic molecular dynamics (MD) simulations of dendrimer conformation in aqueous solutions. The binding measurements show that the HSA binding constants (K(b)) of PAMAM dendrimers depend on dendrimer size and terminal group chemistry. The NMR (1)H and DOSY experiments indicate that the interactions between HSA and PAMAM dendrimers are relatively weak. The (1)H NMR STD experiments and MD simulations suggest that the inner shell protons of the dendrimers groups interact more strongly with HSA proteins. These interactions, which are consistently observed for different dendrimer generations (G0-NH(2)vs G4-NH(2)) and terminal groups (G4-NH(2)vs G4-OH with amidoethanol groups), suggest that PAMAM dendrimers adopt backfolded configurations as they form weak complexes with HSA proteins in aqueous solutions at physiological pH (7.4).

Important role of the non-uniform Fe distribution for the ferromagnetism in group-IV-based ferromagnetic semiconductor GeFe

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wakabayashi, Yuki K.; Ohya, Shinobu; Ban, Yoshisuke

2014-11-07

We investigate the growth-temperature dependence of the properties of the group-IV-based ferromagnetic semiconductor Ge{sub 1−x}Fe{sub x} films (x = 6.5% and 10.5%), and reveal the correlation of the magnetic properties with the lattice constant, Curie temperature (T{sub C}), non-uniformity of Fe atoms, stacking-fault defects, and Fe-atom locations. While T{sub C} strongly depends on the growth temperature, we find a universal relationship between T{sub C} and the lattice constant, which does not depend on the Fe content x. By using the spatially resolved transmission-electron diffractions combined with the energy-dispersive X-ray spectroscopy, we find that the density of the stacking-fault defects and the non-uniformitymore » of the Fe concentration are correlated with T{sub C}. Meanwhile, by using the channeling Rutherford backscattering and particle-induced X-ray emission measurements, we clarify that about 15% of the Fe atoms exist on the tetrahedral interstitial sites in the Ge{sub 0.935}Fe{sub 0.065} lattice and that the substitutional Fe concentration is not correlated with T{sub C}. Considering these results, we conclude that the non-uniformity of the Fe concentration plays an important role in determining the ferromagnetic properties of GeFe.« less

Investigation of flavonoids bearing different substituents on ring C and their cu2+ complex binding with bovine serum albumin: structure-affinity relationship aspects.

PubMed

Shi, Shuyun; Zhang, Yuping; Chen, Xiaoqin; Peng, Mijun

2011-10-12

The effects of 1:1 flavonoid-Cu(2+) complexes of four flavonoids with different C-ring substituents, quercetin (QU), luteolin (LU), taxifolin (TA), and (+)-catechin (CA), on bovine serum albumin (BSA) were investigated and compared with corresponding free flavonoids by spectroscopic analysis in an attempt to characterize the chemical association taking place. The results indicated that all of the quenching mechanisms were based on static quenching combined with nonradiative energy transfer. Cu(2+) chelation changed the binding constants for BSA depending on the structures of flavonoids and the detected concentrations. The reduced hydroxyl groups, increased steric hindrance, and hydrophilicity of Cu(2+) chelation may be the main reasons for the reduced binding constants, whereas the formation of stable flavonoid-Cu(2+) complexes and synergistic action could increase the binding constants. The changed trends of critical energy transfer distance (R(0)) for Cu(2+) chelation were contrary to those of binding constants.

Median statistics estimates of Hubble and Newton's constants

NASA Astrophysics Data System (ADS)

Bethapudi, Suryarao; Desai, Shantanu

2017-02-01

Robustness of any statistics depends upon the number of assumptions it makes about the measured data. We point out the advantages of median statistics using toy numerical experiments and demonstrate its robustness, when the number of assumptions we can make about the data are limited. We then apply the median statistics technique to obtain estimates of two constants of nature, Hubble constant (H0) and Newton's gravitational constant ( G , both of which show significant differences between different measurements. For H0, we update the analyses done by Chen and Ratra (2011) and Gott et al. (2001) using 576 measurements. We find after grouping the different results according to their primary type of measurement, the median estimates are given by H0 = 72.5^{+2.5}_{-8} km/sec/Mpc with errors corresponding to 95% c.l. (2 σ) and G=6.674702^{+0.0014}_{-0.0009} × 10^{-11} Nm2kg-2 corresponding to 68% c.l. (1σ).

Army dependents: childhood illness and health provision.

PubMed

Giles, Sarah

2005-06-01

This small qualitative study explored attitudes of a group of Army wives to childhood illness and their expectations of health provision. The author's practice serves a population mainly comprising of Army dependents where GP attendance rates are double the national average. Two focus groups were organised using health visitor groups attached to the practice. Transcripts were examined to produce a framework for semi-structured interviews with nine mothers, who were selected by purposive sampling. Mothers were asked about symptoms, coping, social problems, decisions to take action, health provision and support. Data were analysed and sorted, using the principles of grounded theory, into four main themes: attitude to child's illness, coping, Army culture and accessibility to health services. Many Army wives appear to suffer from high levels of stress. It seemed that the coping ability of the mother was affected by the constant turbulence and isolation of Army life. While mothers displayed a knowledge of common illnesses, they had fears of the unknown and of life threatening illnesses. They sometimes managed childhood illness at home owing to lack of transport. The author concluded that some Army wives suffer from stress and lack confidence in their mothering skills when their children are ill, which may be due, in part, to the constant cycle of postings and isolation from family and services. They need easily accessible health facilities and information regarding these services. Communication should be encouraged between civilian services and the Army. It appears that Army dependents require more support from their GP practice than the average civilian family, offering opportunity for nurses and health visitors to provide alternative and proactive services.

Physiological and Biochemical Mechanisms of Lifespan Regulation in Rats Kept Under Various Light Conditions.

PubMed

Khizhkin, Evgeniy A; Ilukha, Victor A; Vinogradova, Irina A; Uzenbaeva, Lyudmila B; Ilyina, Tatiana N; Yunash, Victoria D; Morozov, Artem V; Anisimov, Vladimir N

2017-01-01

The present study was aimed to identify how age-related changes in some physiological and biochemical systems are related to changes in the life span of rats with long-term pineal gland hypo- and hyperfunction induced by constant light and constant darkness, respectively. At the age of 25 days the rats were randomly divided into 3 groups: standard light/dark regimen (LD), constant light (LL) and constant darkness (DD). Age-related Antioxidant System (AOS) changes in liver tissues, alteration of immunoreactivity in blood smears were investigated, pubescence and lifespan of the animals were determined. Modification of the level of melatonin synthesis induced by constant light results in interrelated rearrangements in the functioning of the investigated physiological systems. Elevated activity of the antioxidant system extends the lifespan, while at the same time slowing down pubescence and altering the morpho-functional properties of leukocytes in blood. The absence of light/dark alternation (constant light and constant darkness) affects only those physiological indices that follow the organism's circadian rhythms (Activity of Antioxidant Enzymes (AOE), levels of individual immune system cell types), whereas changes in the parameters not governed by circadian fluctuations (vitamin concentrations, pubescence, and aging) depend on the level of melatonin produced by the pineal gland.

Methane steam reforming rates over Pt, Rh and Ni(111) accounting for H tunneling and for metal lattice vibrations

NASA Astrophysics Data System (ADS)

German, Ernst D.; Sheintuch, Moshe

2017-02-01

Microkinetic models of methane steam reforming (MSR) over bare platinum and rhodium (111) surfaces are analyzed in present work using calculated rate constants. The individual rate constants are classified into three different sets: (i) rate constants of adsorption and desorption steps of CH4, H2O, CO and of H2; (ii) rate constants of dissociation and formation of A-H bonds (A = C, O, and H), and (iii) rate constants of dissociation and formation of C-O bond. The rate constants of sets (i) and (iii) are calculated using transition state theory and published thermochemical data. The rate constants of H-dissociation reactions (set (ii)) are calculated in terms of a previously-developed approach that accounts for thermal metal lattice vibrations and for H tunneling through a potential barrier of height which depends on distance of AH from a surface. Pre-exponential factors of several group (ii) steps were calculated to be usually lower than the traditional kBT/h due to tunneling effect. Surface composition and overall MSR rates over platinum and rhodium surfaces are compared with those over nickel surface showing that operating conditions strongly affect on the activity order of the catalysts.

The sensitivity of numerically simulated climates to land-surface boundary conditions

NASA Technical Reports Server (NTRS)

Mintz, Y.

1982-01-01

Eleven sensitivity experiments that were made with general circulation models to see how land-surface boundary conditions can influence the rainfall, temperature, and motion fields of the atmosphere are discussed. In one group of experiments, different soil moistures or albedos are prescribed as time-invariant boundary conditions. In a second group, different soil moistures or different albedos are initially prescribed, and the soil moisture (but not the albedo) is allowed to change with time according to the governing equations for soil moisture. In a third group, the results of constant versus time-dependent soil moistures are compared.

Rate Constant and Temperature Dependence for the Reaction of Hydroxyl Radicals with 2-Flouropropane (FC-281ea) and Comparison with an Estimated Rate Constant

NASA Technical Reports Server (NTRS)

DeMore, W.; Wilson, E., Jr.

1998-01-01

Relative rate experiments were used to measure the rate constant and temperature dependence of the reaction of OH radicals with 2-fluoropropane (HFC-281ea), using ethane, propane, ethyl chloride as reference standards.

Temperature dependence of (+)-catechin pyran ring proton coupling constants as measured by NMR and modeled using GMMX search methodology

Treesearch

Fred L. Tobiason; Stephen S. Kelley; M. Mark Midland; Richard W. Hemingway

1997-01-01

The pyran ring proton coupling constants for (+)-catechin have been experimentally determined in deuterated methanol over a temperature range of 213 K to 313 K. The experimental coupling constants were simulated to 0.04 Hz on the average at a 90 percent confidence limit using a LAOCOON method. The temperature dependence of the coupling constants was reproduced from the...

How Much Power Does a Higher Ed Institution Have over Including Transgender Students in Greek Life?

ERIC Educational Resources Information Center

Nguyen, AiVi

2016-01-01

Different images come to mind when thinking about college fraternities and sororities, depending on who you are. Whether your images are positive or negative, one thing is constant: You envision a group of same-sex young people. But one of the major social issues that this country is dealing with is the treatment of transgender people, and…

Cl(-) concentration dependence of photovoltage generation by halorhodopsin from Halobacterium salinarum.

PubMed Central

Muneyuki, Eiro; Shibazaki, Chie; Wada, Yoichiro; Yakushizin, Manabu; Ohtani, Hiroyuki

2002-01-01

The photovoltage generation by halorhodopsin from Halobacterium salinarum (shR) was examined by adsorbing shR-containing membranes onto a thin polymer film. The photovoltage consisted of two major components: one with a sub-millisecond range time constant and the other with a millisecond range time constant with different amplitudes, as previously reported. These components exhibited different Cl(-) concentration dependencies (0.1-9 M). We found that the time constant for the fast component was relatively independent of the Cl(-) concentration, whereas the time constant for the slow component increased sigmoidally at higher Cl(-) concentrations. The fast and the slow processes were attributed to charge (Cl(-)) movements within the protein and related to Cl(-) ejection, respectively. The laser photolysis studies of shR-membrane suspensions revealed that they corresponded to the formation and the decay of the N intermediate. The photovoltage amplitude of the slow component exhibited a distorted bell-shaped Cl(-) concentration dependence, and the Cl(-) concentration dependence of its time constant suggested a weak and highly cooperative Cl(-)-binding site(s) on the cytoplasmic side (apparent K(D) of approximately 5 M and Hill coefficient > or =5). The Cl(-) concentration dependence of the photovoltage amplitude and the time constant for the slow process suggested a competition between spontaneous relaxation and ion translocation. The time constant for the relaxation was estimated to be >100 ms. PMID:12324398

Henry's law constants of polyols

NASA Astrophysics Data System (ADS)

Compernolle, S.; Müller, J.-F.

2014-12-01

Henry's law constants (HLC) are derived for several polyols bearing between 2 and 6 hydroxyl groups, based on literature data for water activity, vapour pressure and/or solubility. While deriving HLC and depending on the case, also infinite dilution activity coefficients (IDACs), solid state vapour pressures or activity coefficient ratios are obtained as intermediate results. An error analysis on the intermediate quantities and the obtained HLC is included. For most compounds, these are the first values reported, while others compare favourably with literature data in most cases. Using these values and those from a previous work (Compernolle and Müller, 2014), an assessment is made on the partitioning of polyols, diacids and hydroxy acids to droplet and aqueous aerosol.

New Fluorescent Macrolide Derivatives for Studying Interactions of Antibiotics and Their Analogs with the Ribosomal Exit Tunnel.

PubMed

Tereshchenkov, A G; Shishkina, A V; Karpenko, V V; Chertkov, V A; Konevega, A L; Kasatsky, P S; Bogdanov, A A; Sumbatyan, N V

2016-10-01

Novel fluorescent derivatives of macrolide antibiotics related to tylosin bearing rhodamine, fluorescein, Alexa Fluor 488, BODIPY FL, and nitrobenzoxadiazole (NBD) residues were synthesized. The formation of complexes of these compounds with 70S E. coli ribosomes was studied by measuring the fluorescence polarization depending on the ribosome amount at constant concentration of the fluorescent substance. With the synthesized fluorescent tylosin derivatives, the dissociation constants for ribosome complexes with several known antibiotics and macrolide analogs previously obtained were determined. It was found that the fluorescent tylosin derivatives containing BODIPY FL and NBD groups could be used to screen the binding of novel antibiotics to bacterial ribosomes in the macrolide-binding site.

Investigation of the acid-base and electromigration properties of 5-azacytosine derivatives using capillary electrophoresis and density functional theory calculations.

PubMed

Geffertová, Denisa; Ali, Syed Tahir; Šolínová, Veronika; Krečmerová, Marcela; Holý, Antonín; Havlas, Zdeněk; Kašička, Václav

2017-01-06

Capillary electrophoresis (CE) and quantum mechanical density functional theory (DFT) were applied to the investigation of the acid-base and electromigration properties of important compounds: newly synthesized derivatives of 5-azacytosine - analogs of efficient antiviral drug cidofovir. These compounds exhibit a strong antiviral activity and they are considered as potential new antiviral agents. For their characterization and application, it is necessary to know their acid-base properties, particularly the acidity constants (pK a ) of their ionogenic groups (the basic N 3 atom of the triazine ring and the acidic phosphonic acid group in the alkyl chain). First, the mixed acidity constants (pK a mix ) of these ionogenic groups and the ionic mobilities of these compounds were determined by nonlinear regression analysis of the pH dependence of their effective electrophoretic mobilities. Effective mobilities were measured by CE in a series of background electrolytes in a wide pH range (2.0-10.5), at constant ionic strength (25mM) and constant temperature (25°C). Subsequently, the pK a mix values were recalculated to thermodynamic pK a values using the Debye-Hückel theory. The thermodynamic pK a value of the NH + moiety at the N 3 atom of the triazine ring was found to be in the range 2.82-3.30, whereas the pK a of the hydrogenphosphonate group reached values from 7.19 to 7.47, depending on the structure of the analyzed compounds. These experimentally determined pK a values were in good agreement with those calculated by quantum mechanical DFT. In addition, DFT calculations revealed that from the four nitrogen atoms in the 5-azacytosine moiety, the N 3 atom of the triazine ring is preferentially protonated. Effective charges of analyzed compounds ranged from zero or close-to-zero values at pH 2 to -2 elementary charges at pH≥9. Ionic mobilities were in the range (-16.7 to -19.1)×10 -9 m 2 V -1 s -1 for univalent anions and in the interval (-26.9 to -30.3)×10 -9 m 2 V -1 s -1 for divalent anions. Copyright © 2016 Elsevier B.V. All rights reserved.

Non-Friedmann cosmology for the Local Universe, significance of the universal Hubble constant, and short-distance indicators of dark energy

NASA Astrophysics Data System (ADS)

Chernin, A. D.; Teerikorpi, P.; Baryshev, Yu. V.

2006-09-01

Based on the increasing evidence of the cosmological relevance of the local Hubble flow, we consider a simple analytical cosmological model for the Local Universe. This is a non-Friedmann model with a non-uniform static space-time. The major dynamical factor controlling the local expansion is the antigravity produced by the omnipresent and permanent dark energy of the cosmic vacuum (or the cosmological constant). The antigravity dominates at larger distances than 1-2 Mpc from the center of the Local group. The model gives a natural explanation of the two key quantitative characteristics of the local expansion flow, which are the local Hubble constant and the velocity dispersion of the flow. The observed kinematical similarity of the local and global flows of expansion is clarified by the model. We analytically demonstrate the efficiency of the vacuum cooling mechanism that allows one to see the Hubble law this close to the Local group. The "universal Hubble constant" HV (≈60 km s-1 Mpc-1), depending only on the vacuum density, has special significance locally and globally. The model makes a number of verifiable predictions. It also unexpectedly shows that the dwarf galaxies of the local flow with the shortest distances and lowest redshifts may be the most sensitive indicators of dark energy in our neighborhood.

Transfer of motor learning engages specific neural substrates during motor memory consolidation dependent on the practice structure.

PubMed

Kantak, Shailesh S; Sullivan, Katherine J; Fisher, Beth E; Knowlton, Barbara J; Winstein, Carolee J

2011-01-01

The authors investigated how brain activity during motor-memory consolidation contributes to transfer of learning to novel versions of a motor skill following distinct practice structures. They used 1 Hz repetitive Transcranial Magnetic Stimulation (rTMS) immediately after constant or variable practice of an arm movement skill to interfere with primary motor cortex (M1) or dorsolateral prefrontal cortex (DLPFC). The effect of interference was assessed through skill performance on two transfer targets: one within and one outside the range of practiced movement parameters for the variable practice group. For the control (no rTMS) group, variable practice benefited delayed transfer performance more than constant practice. The rTMS effect on delayed transfer performance differed for the two transfer targets. For the within-range target, rTMS interference had no significant affect on the delayed transfer after either practice structure. However, for the outside-range target, rTMS interference to DLPFC but not M1 attenuated delayed transfer benefit following variable practice. Additionally, for the outside-range target, rTMS interference to M1 but not DLPFC attenuated delayed transfer following constant practice. This suggests that variable practice may promote reliance on DLPFC for memory consolidation associated with outside-range transfer of learning, whereas constant practice may promote reliance on M1 for consolidation and long-term transfer.

Microwave Spectra of the Two Conformers of PROPENE-3-{d}_1 and a Semiexperimental Equilibrium Structure of Propene

NASA Astrophysics Data System (ADS)

Craig, Norman C.; Demaison, J.; Rudolph, Heinz Dieter; Gurusinghe, Ranil M.; Tubergen, Michael; Coudert, L. H.; Szalay, Peter; Császár, Attila

2017-06-01

FT microwave spectra have been observed and analyzed for the S (in-plane) and A (out-of-plane) conformers of propene-3-{d}_1 in the 10-22 GHz region. Both conformers display splittings due to deuterium quadrupole coupling; for the latter one only, a 19 MHz splitting due to internal rotation of the partially deuterated methyl group has been observed. In addition to rotational constants, the analysis yielded quadrupole coupling constants and parameters describing the tunneling splitting and its rotational dependence. Improved rotational constants for parent propene and the three ^{13}C_1 species are recently available. Use of vibration-rotation interaction constants computed at the MP2(FC)/cc-pVTZ level gave equilibrium rotational constants for these six species and for fourteen more deuterium isotopologues with diminished accuracy from early literature data. A semiexperimental equilibrium structure, r_e^{SE}, has been determined for propene by fitting fourteen structural parameters to the equilibrium rotational constants. The new r_e^{SE} structure compares well with an ab initio equilibrium structure computed with the all-electron CCSD(T)/cc-pV(Q,T)Z model and with a structure obtained using the mixed regression method with predicates and equilibrium rotational constants. N. C. Craig, P. Groner, A. R. Conrad, R. Gurusinghe, M. J. Tubergen J. Mol. Spectrosc. 248, 1-6 (2016).

Sorption of certain isatins on various sorbents under RP-HPLC conditions

NASA Astrophysics Data System (ADS)

Konstantinov, A. V.; Shafigulin, R. V.; Il'in, M. M.; Davankov, V. A.; Bulanova, A. V.; Purygin, P. P.

2013-06-01

The results from chromatographic analysis of biologically active isatin derivatives on hyper-crosslinked polystyrene (HCLPS) and silica gel modified by octadecyl groups (SilC18) are presented. The constants of distribution of sorbates between a mobile phase and the investigated sorbents ( K x ) and the changes in the standard differential molar Gibbs energies of adsorption (Δ _a bar G^circ ) are calculated, along with the chromatographic retention-physicochemical property of sorbate dependences. It is found that the equations describing these dependences have high forecasting ability with respect to the values of retention factors of the investigated sorbates.

GABA-benzodiazepine receptor function in alcohol dependence: a combined 11C-flumazenil PET and pharmacodynamic study.

PubMed

Lingford-Hughes, A R; Wilson, S J; Cunningham, V J; Feeney, A; Stevenson, B; Brooks, D J; Nutt, D J

2005-08-01

Gamma-aminobutyric acid (GABA)-benzodiazepine receptor function is hypothesised to be reduced in alcohol dependence. We used positron emission tomography (PET) with [11C]flumazenil, a non-selective tracer for brain GABA-benzodiazepine (GABA-BDZ) receptor binding, to determine in vivo the relationship between BDZ receptor occupancy by an agonist, midazolam, and its functional effects. Abstinent male alcohol dependent subjects underwent [11C]flumazenil PET to measure occupancy of BDZ receptors by midazolam whilst recording its pharmacodynamic effects on behavioural and physiological measures. Rate constants describing the exchange of [11C]flumazenil between the plasma and brain compartments were derived from time activity curves. A 50% reduction in electroencephalography (EEG)-measured sleep time was seen in the alcohol dependent group despite the same degree of occupancy by midazolam as seen in the control group. The effects of midazolam on other measures of benzodiazepine receptor function, increasing EEG beta1 power and slowing of saccadic eye movements, were similar in the two groups. No differences in midazolam or flumazenil metabolism were found between the groups. In summary, our study suggests that alcohol dependence in man is associated with a reduced EEG sleep response to the benzodiazepine agonist, midazolam, which is not explained by reduced BDZ receptor occupancy, and is consistent with reduced sensitivity in this measure of GABA-BDZ receptor function in alcohol dependence. The lack of change in other functional measures may reflect a differential involvement of particular subtypes of the GABA-BDZ receptor.

Temperature Dependence Of Elastic Constants Of Polymers

NASA Technical Reports Server (NTRS)

Simha, Robert; Papazoglou, Elisabeth

1989-01-01

Two papers extend theory of elastic constants of disordered solids to finite temperatures below glass-transition temperatures. First paper, entitled "Elastic Constants of Disordered Solids II: Temperature Dependence," applies to cryogenic temperatures. Second paper, entitled "Theory of Thermoelastic Properties for Polymer Glasses," develops unified treatment for static compressional and elongational properties at temperatures up to glass-transition temperatures.

A Simple Method to Calculate the Temperature Dependence of the Gibbs Energy and Chemical Equilibrium Constants

ERIC Educational Resources Information Center

Vargas, Francisco M.

2014-01-01

The temperature dependence of the Gibbs energy and important quantities such as Henry's law constants, activity coefficients, and chemical equilibrium constants is usually calculated by using the Gibbs-Helmholtz equation. Although, this is a well-known approach and traditionally covered as part of any physical chemistry course, the required…

Complex methyl group and hydrogen-bonded proton motions in terms of the Arrhenius and Schrödinger equations.

PubMed

Latanowicz, L

2008-01-01

Equations for the temperature dependence of the spectral densities J(is)(m)(momega(I) +/-omega(T)), where m=1, 2, omega(I) and omega(T) are the resonance and tunnel splitting angular frequencies, in the presence of a complex motion, have been derived. The spin pairs of the protons or deuterons of the methyl group perform a complex motion consisting of three component motions. Two of them involve mass transportation over the barrier and through the barrier. They are characterized by k((H)) (Arrhenius) and k((T)) (Schrödinger) rate constants, respectively. The third motion causes fluctuations of the frequencies (nomega(I)+/-omega(T)) and it is related to the lifetime of the methyl spin at the energy level influenced by the rotor-bath interactions. These interactions induce rapid transitions, changing the symmetry of the torsional sublevels either from A to E or from E(a) to E(b). The correlation function for this third motion (k((omega)) rate constant) has been proposed by Müller-Warmuth et al. The spectral densities of the methyl group hindered rotation (k((H)), k((T)) and k((omega)) rate constants) differ from the spectral densities of the proton transfer (k((H)) and k((T)) rate constants) because three compound motions contribute to the complex motion of the methyl group. The recently derived equation [Formula: see text] , where [Formula: see text] and [Formula: see text] are the fraction and energy of particles with energies from zero to E(H), is taken into account in the calculations of the spectral densities. This equation follows from Maxwell's distribution of thermal energy. The spectral densities derived are applied to analyse the experimental temperature dependencies of proton and deuteron spin-lattice relaxation rate in solids containing the methyl group. A wide range of temperatures from zero Kelvin up to the melting point is considered. It has been established that the motion characterized by k((omega)) influences the spin-lattice relaxation up to the temperature T(tun) only. This temperature is directly determined by the equation C(p)T=E(H) (thermal energy=activation energy), where C(p) is the molar heat capacity. Probably the cessation of the third motion is a result of the de Broglie wavelength related to this motion becoming too short. As shown recently, the potential barrier can be an obstacle for the de Broglie wave. The theoretical equations derived in this paper are compared to those known in the literature.

Centrifugal distortion and the ring puckering vibration in the microwave spectrum of 2,3-dihydrofuran

NASA Astrophysics Data System (ADS)

Cervellati, R.; Degli Esposti, A.; Lister, D. G.; Lopez, J. C.; Alonso, J. L.

1986-10-01

The microwave spectrum of 2,3-dihydrofuran has been reinvestigated and measurements for the ground and first five excited states of the ring puckering vibration have been extended to higher frequencies and rotational quantum numbers in order to study the vibrational dependence of the rotational and centrifugal distortion constants. The ring puckering potential function derived by Green from the far infrared spectrum does not reproduce the vibrational dependence of the rotational constants well. A slightly different potential function is derived which gives a reasonable fit both to the far infrared spectrum and the rotational constants. This changes the barrier to ring inversion from 1.00 kJ mol -1 to 1.12 kJ mol -1. The vibrational dependence of the centrifugal distortion constants is accounted for satisfactorily by the theory developed by Creswell and Mills. An attempt to reproduce the vibrational dependence of the rotational and centrifugal distortion constants using the ring puckering potential function and a simple model for this vibration has very limited success.

Exciplex-like emission from a closely-spaced, orthogonally-sited anthracenyl-boron dipyrromethene (Bodipy) molecular dyad.

PubMed

Benniston, Andrew C; Harriman, Anthony; Whittle, Victoria L; Zelzer, Mischa; Harrington, Ross W; Clegg, William

2010-07-30

A molecular dyad, , has been prepared that incorporates a boron dipyrromethene (Bodipy) group functionalized at the meso position with an anthracenyl unit. Emission from the dyad contains contributions from both localized fluorescence from the Bodipy unit and exciplex-like emission associated with an intramolecular charge-transfer state. The peak position, intensity and lifetime of this exciplex emission are solvent dependent and the shift in the emission maximum shows a linear relationship to the solvent polarity function (Deltaf). The calculated dipole moment for the exciplex is 22.5 +/- 2.2 D. The radiative rate constant (k(RAD)) for exciplex emission decreases progressively with increasing solvent polarity. In this latter case, k(RAD) shows an obvious dependence on the energy gap between the exciplex state and the first-excited singlet state resident on the Bodipy unit. The emission characteristics for dissolved in perfluorooctane are used to characterize the refractive index and dielectric constant of the solvent.

Molecular dynamics studies of a DNA-binding protein: 2. An evaluation of implicit and explicit solvent models for the molecular dynamics simulation of the Escherichia coli trp repressor.

PubMed Central

Guenot, J.; Kollman, P. A.

1992-01-01

Although aqueous simulations with periodic boundary conditions more accurately describe protein dynamics than in vacuo simulations, these are computationally intensive for most proteins. Trp repressor dynamic simulations with a small water shell surrounding the starting model yield protein trajectories that are markedly improved over gas phase, yet computationally efficient. Explicit water in molecular dynamics simulations maintains surface exposure of protein hydrophilic atoms and burial of hydrophobic atoms by opposing the otherwise asymmetric protein-protein forces. This properly orients protein surface side chains, reduces protein fluctuations, and lowers the overall root mean square deviation from the crystal structure. For simulations with crystallographic waters only, a linear or sigmoidal distance-dependent dielectric yields a much better trajectory than does a constant dielectric model. As more water is added to the starting model, the differences between using distance-dependent and constant dielectric models becomes smaller, although the linear distance-dependent dielectric yields an average structure closer to the crystal structure than does a constant dielectric model. Multiplicative constants greater than one, for the linear distance-dependent dielectric simulations, produced trajectories that are progressively worse in describing trp repressor dynamics. Simulations of bovine pancreatic trypsin were used to ensure that the trp repressor results were not protein dependent and to explore the effect of the nonbonded cutoff on the distance-dependent and constant dielectric simulation models. The nonbonded cutoff markedly affected the constant but not distance-dependent dielectric bovine pancreatic trypsin inhibitor simulations. As with trp repressor, the distance-dependent dielectric model with a shell of water surrounding the protein produced a trajectory in better agreement with the crystal structure than a constant dielectric model, and the physical properties of the trajectory average structure, both with and without a nonbonded cutoff, were comparable. PMID:1304396

Effects of Constant Flow vs. Constant Pressure Perfusion on Fluid Filtration in Severe Hypothermic Isolated Blood-Perfused Rat Lungs.

PubMed

Halsøy, Kathrine; Kondratiev, Timofey; Tveita, Torkjel; Bjertnaes, Lars J

2016-01-01

Victims of severe accidental hypothermia are prone to fluid extravasation but rarely develop lung edema. We hypothesize that combined hypothermia-induced increase in pulmonary vascular resistance (PVR) and a concomitant fall in cardiac output protect the lungs against edema development. Our aim was to explore in hypothermic-isolated blood-perfused rat lungs whether perfusion at constant pressure influences fluid filtration differently from perfusion at constant flow. Isolated blood-perfused rat lungs were hanging freely in a weight transducer for measuring weight changes (ΔW). Fluid filtration coefficient (Kfc), was determined by transiently elevating left atrial pressure (Pla) by 5.8 mmHg two times each during normothermia (37°C) and during hypothermia (15°C). The lung preparations were randomized to two groups. One group was perfused with constant flow (Constant flow group) and the other group with constant pulmonary artery pressure (Constant PPA group). Microvascular pressure (Pmv) was determined before and during elevation of Pla (ΔPmv) by means of the double occlusion technique. Kfc was calculated with the formula Kfc = ΔW/ΔPmv/min. All Kfc values were normalized to predicted lung weight (P LW ), which was based on body weight (BW) according to the formula: P LW  = 0.0053 BW - 0.48 and presented as Kfc PLW in mg/min/mmHg/g. At cessation, bronchoalveolar lavage (BAL) fluid/perfusate protein concentration (B/P) ratio was determined photometrically. Data were analyzed with parametric or non-parametric tests as appropriate. p  < 0.05 considered as significant. Perfusate flow remained constant in the Constant flow group, but was more than halved during hypothermia in the Constant PPA group concomitant with a more fold increase in PVR. In the Constant flow group, Kfc PLW and B/P ratio increased significantly by more than 10-fold during hypothermia concerted by visible signs of edema in the trachea. Hemoglobin and hematocrit increased within the Constant flow group and between the groups at cessation of the experiments. In hypothermic rat lungs perfused at constant flow, fluid filtration coefficient per gram P LW and B/P ratio increased more than 10-fold concerted by increased hemoconcentration, but the changes were less in hypothermic lungs perfused at constant PPA.

Pulse echo and combined resonance techniques: a full set of LGT acoustic wave constants and temperature coefficients.

PubMed

Sturtevant, Blake T; Davulis, Peter M; da Cunha, Mauricio Pereira

2009-04-01

This work reports on the determination of langatate elastic and piezoelectric constants and their associated temperature coefficients employing 2 independent methods, the pulse echo overlap (PEO) and a combined resonance technique (CRT) to measure bulk acoustic wave (BAW) phase velocities. Details on the measurement techniques are provided and discussed, including the analysis of the couplant material in the PEO technique used to couple signal to the sample, which showed to be an order of magnitude more relevant than the experimental errors involved in the data extraction. At room temperature, elastic and piezoelectric constants were extracted by the PEO and the CRT methods and showed results consistent to within a few percent for the elastic constants. Both raw acquired data and optimized constants, based on minimization routines applied to all the modes involved in the measurements, are provided and discussed. Comparison between the elastic constants and their temperature behavior with the literature reveals the recent efforts toward the consistent growth and characterization of LGT, in spite of significant variations (between 1 and 30%) among the constants extracted by different groups at room temperature. The density, dielectric permittivity constants, and respective temperature coefficients used in this work have also been independently determined based on samples from the same crystal boule. The temperature behavior of the BAW modes was extracted using the CRT technique, which has the advantage of not relying on temperature dependent acoustic couplants. Finally, the extracted temperature coefficients for the elastic and piezoelectric constants between room temperature and 120 degrees C are reported and discussed in this work.

Kinetics and Mechanism Study of Competitive Inhibition of Jack-Bean Urease by Baicalin

PubMed Central

Tan, Lirong; Su, Jiyan; Wu, Dianwei; Yu, Xiaodan; Su, Zuqing; Wu, Xiaoli; Kong, Songzhi; Lai, Xiaoping; Lin, Ji; Su, Ziren

2013-01-01

Baicalin (BA) is the principal component of Radix Scutellariae responsible for its pharmacological activity. In this study, kinetics and mechanism of inhibition by BA against jack-bean urease were investigated for its therapeutic potential. It was revealed that the IC50 of BA against jack-bean urease was 2.74 ± 0.51 mM, which was proved to be a competitive and concentration-dependent inhibition with slow-binding progress curves. The rapid formation of initial BA-urease complex with an inhibition constant of K i = 3.89 × 10−3 mM was followed by a slow isomerization into the final complex with an overall inhibition constant of K i* = 1.47 × 10−4 mM. High effectiveness of thiol protectors against BA inhibition indicated that the strategic role of the active-site sulfhydryl group of the urease was involved in the blocking process. Moreover, the inhibition of BA was proved to be reversible due to the fact that urease could be reactivated by dithiothreitol but not reactant dilution. Molecular docking assay suggested that BA made contacts with the important activating sulfhydryl group Cys-592 residues and restricted the mobility of the active-site flap. Taken together, it could be deduced that BA was a competitive inhibitor targeting thiol groups of urease in a slow-binding manner both reversibly and concentration-dependently, serving as a promising urease inhibitor for treatments on urease-related diseases. PMID:24198731

Determination of the Temperature Dependence of Heat Capacity for Some Molecular Crystals of Nitro Compounds

NASA Astrophysics Data System (ADS)

Kovalev, Yu. M.; Kuropatenko, V. F.

2018-05-01

An analysis of the existing approximations used for describing the dependence of heat capacity at a constant volume on the temperature of a molecular crystal has been carried out. It is shown that the considered Debye and Einstein approximations do not enable one to adequately describe the dependence of heat capacity at a constant volume on the temperature of the molecular crystals of nitro compounds. This inference requires the development of special approximations that would describe both low-frequency and high-frequency parts of the vibrational spectra of molecular crystals. This work presents a universal dependence allowing one to describe the dependence of heat capacity at a constant volume on temperature for a number of molecular crystals of nitro compounds.

Heat capacity of molten halides.

PubMed

Redkin, Alexander A; Zaikov, Yurii P; Korzun, Iraida V; Reznitskikh, Olga G; Yaroslavtseva, Tatiana V; Kumkov, Sergey I

2015-01-15

The heat capacities of molten salts are very important for their practical use. Experimental investigation of this property is challenging because of the high temperatures involved and the corrosive nature of these materials. It is preferable to combine experimental investigations with empirical relationships, which allows for the evaluation of the heat capacity of molten salt mixtures. The isobaric molar heat capacities of all molten alkali and alkaline-earth halides were found to be constant for each group of salts. The value depends on the number of atoms in the salt, and the molar heat capacity per atom is constant for all molten halide salts with the exception of the lithium halides. The molar heat capacities of molten halides do not change when the anions are changed.

Elastic Constants of Ni-Mn-Ga Magnetic Shape Memory Alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stipcich, M.; Manosa, L.; Planes, A.

2004-01-01

We have measured the adiabatic second order elastic constants of two Ni-Mn-Ga magnetic shape memory crystals with different martensitic transition temperatures, using ultrasonic methods. The temperature dependence of the elastic constants has been followed across the ferromagnetic transition and down to the martensitic transition temperature. Within experimental errors no noticeable change in any of the elastic constants has been observed at the Curie point. The temperature dependence of the shear elastic constant C' has been found to be very different for the two alloys. Such a different behavior is in agreement with recent theoretical predictions for systems undergoing multi-stage structuralmore » transitions.« less

Modeling of Internet Influence on Group Emotion

NASA Astrophysics Data System (ADS)

Czaplicka, Agnieszka; Hołyst, Janusz A.

Long-range interactions are introduced to a two-dimensional model of agents with time-dependent internal variables ei = 0, ±1 corresponding to valencies of agent emotions. Effects of spontaneous emotion emergence and emotional relaxation processes are taken into account. The valence of agent i depends on valencies of its four nearest neighbors but it is also influenced by long-range interactions corresponding to social relations developed for example by Internet contacts to a randomly chosen community. Two types of such interactions are considered. In the first model the community emotional influence depends only on the sign of its temporary emotion. When the coupling parameter approaches a critical value a phase transition takes place and as result for larger coupling constants the mean group emotion of all agents is nonzero over long time periods. In the second model the community influence is proportional to magnitude of community average emotion. The ordered emotional phase was here observed for a narrow set of system parameters.

Large birefringence and polarization holographic gratings formed in photocross-linkable polymer liquid crystals comprising bistolane mesogenic side groups

NASA Astrophysics Data System (ADS)

Emoto, Akira; Matsumoto, Taro; Yamashita, Ayumi; Shioda, Tatsutoshi; Ono, Hiroshi; Kawatsuki, Nobuhiro

2009-10-01

Polarization gratings with large birefringence are formed in photoreactive polymer liquid crystals with bistolane moiety and terminal cinnamic acid moiety by the use of polarized ultraviolet interference light and subsequent annealing. The polarized ultraviolet light causes the axis-selective photoreaction between the cinnamic acid groups and subsequent annealing induce the reorientation of peripheral molecules without cross-linking along the cross-linked groups. Long bistolane mesogenic moiety exhibits large birefringence in comparison with a biphenyl mesogenic moiety, the value of the induced birefringence in the bistolane mesogenic liquid crystalline (LC) polymer is strongly dependent on both the grating constant and the wavelength of the reconstruction light.

The structural and electronical factors that contribute affinity for the time-dependent inhibition of PGHS-1 by indomethacin, diclofenac and fenamates

NASA Astrophysics Data System (ADS)

Pouplana, R.; Pérez, C.; Sánchez, J.; Lozano, J. J.; Puig-Parellada, P.

1999-05-01

PGHS-1 and PGHS-2 are the targets of nonsteroidal anti- inflammatory drugs (NSAIDs). It appears that the high degree of selectivity for inhibition of PGHS-2 shown by certain compounds is the result of two mechanisms (time-dependent and time-independent inhibition), by which they interact with each isoform. The fenamic acids can be divided into competitive inhibitors of substrate binding and competitive inhibitors that cause time-dependent losses of cyclooxygenase activity. The cyclooxygenase activity was measured by oxygen consumption following preincubation of the enzyme and the inhibitor for increasing periods of time. The rate constants associated with binding inhibition kinetics and structure-activity relationships were calculated for a large number of fenamates, diclofenac and indomethacin. The KI* values are similar but the individual rate constants are markedly different: KI is two-fold lower, and k2 is six-fold slower for diclofenac than for indomethacin. All the active time-dependent compounds show MEPs with a negative conical surface, with their vertex on the minimum of the carboxyl group, which extends around the first aromatic ring to the central region. The conical surface keeps an open angle of 61° or larger, and a close contact surface with the residues Ala527, Ileu523, Val349, and Ser530, in the zones surrounding the bridging amino group and the chlorine atoms for meclofenamate and diclofenac, or in the region around the carbonyl group for indomethacin. The KI* and IC50 values indicate that the interactions that promote the slow binding kinetics must be examined in relation to the reaction energies of formation (ΔHr) of an ionic bond between the deprotonated carboxylic acid group of acid NSAIDs with the monocationic guanidinum group of Arg120, the free energies of solvation in aqueous solution, and the molecular volumes measured. Presumably indomethacin, diclofenac and meclofenamate cause the enzyme to undergo a subtle conformational change to a form that binds compounds even more tightly, with some slight structural changes confined to reorientations of the Arg277 and Gln358 side chains. These results show that the model has reliably chosen regions of biological significance consistent with both the X-ray crystallographic and kinetic results.

Kinetics of binding of chicken cystatin to papain.

PubMed

Björk, I; Alriksson, E; Ylinenjärvi, K

1989-02-21

The kinetics of binding of chicken cystatin to papain were studied by stopped-flow fluorometry under pseudo-first-order conditions, i.e., with an excess of inhibitor. All reactions showed first-order behavior, and the observed pseudo-first-order rate constant increased linearly with the cystatin concentration up to the highest concentration that could be studied, 35 microM. The analyses thus provided no evidence for a limiting rate resulting from a conformational change stabilizing an initial encounter complex, in contrast with previous studies of reactions between serine proteinases and their protein inhibitors. The second-order association rate constant for complex formation was 9.9 X 10(6) M-1 s-1 at 25 degrees C, pH 7.4, I = 0.15, for both forms of cystatin, 1 and 2. This value approaches that expected for a diffusion-controlled rate. The temperature dependence of the association rate constant gave an enthalpy of activation at 25 degrees C of 31.5 kJ mol-1 and an entropy of activation at 25 degrees C of -7 J K-1 mol-1, compatible with no appreciable conformational change during the reaction. The association rate constant was independent of pH between pH 6 and 8 but decreased at lower and higher pH in a manner consistent with involvement of an unprotonated acid group with a pKa of 4-4.5 and a protonated basic group with a pKa of 9-9.5 in the interaction. The association rate constant was unaffected by ionic strengths between 0.15 and 1.0 but decreased somewhat at lower ionic strengths. Incubation of the complex between cystatin 2 and papain with an excess of cystatin 1 resulted in slow displacement of cystatin 2 from the complex.(ABSTRACT TRUNCATED AT 250 WORDS)

Equilibrium constants and protonation site for N-methylbenzenesulfonamides

PubMed Central

Rosa da Costa, Ana M; García-Río, Luis; Pessêgo, Márcia

2011-01-01

Summary The protonation equilibria of four substituted N-methylbenzenesulfonamides, X-MBS: X = 4-MeO (3a), 4-Me (3b), 4-Cl (3c) and 4-NO2 (3d), in aqueous sulfuric acid were studied at 25 °C by UV–vis spectroscopy. As expected, the values for the acidity constants are highly dependent on the electron-donor character of the substituent (the pK BH+ values are −3.5 ± 0.2, −4.2 ± 0.2, −5.2 ± 0.3 and −6.0 ± 0.3 for 3a, 3b, 3c and 3d, respectively). The solvation parameter m* is always higher than 0.5 and points to a decrease in the importance of solvation on the cation stabilization as the electron-donor character of the substituent increases. Hammett plots of the equilibrium constants showed a better correlation with the σ+ substituent parameter than with σ, which indicates that the initial protonation site is the oxygen atom of the sulfonyl group. PMID:22238552

Site- and species-specific hydrolysis rates of heroin.

PubMed

Szöcs, Levente; Orgován, Gábor; Tóth, Gergő; Kraszni, Márta; Gergó, Lajos; Hosztafi, Sándor; Noszál, Béla

2016-06-30

The hydroxide-catalyzed non-enzymatic, simultaneous and consecutive hydrolyses of diacetylmorphine (DAM, heroin) are quantified in terms of 10 site- and species-specific rate constants in connection with also 10 site- and species-specific acid-base equilibrium constants, comprising all the 12 coexisting species in solution. This characterization involves the major and minor decomposition pathways via 6-acetylmorphine and 3-acetylmorphine, respectively, and morphine, the final product. Hydrolysis has been found to be 18-120 times faster at site 3 than at site 6, depending on the status of the amino group and the rest of the molecule. Nitrogen protonation accelerates the hydrolysis 5-6 times at site 3 and slightly less at site 6. Hydrolysis rate constants are interpreted in terms of intramolecular inductive effects and the concomitant local electron densities. Hydrolysis fraction, a new physico-chemical parameter is introduced and determined to quantify the contribution of the individual microspecies to the overall hydrolysis. Hydrolysis fractions are depicted as a function of pH. Copyright © 2016 Elsevier B.V. All rights reserved.

Size and molecular flexibility affect the binding of ellagitannins to bovine serum albumin.

PubMed

Dobreva, Marina A; Green, Rebecca J; Mueller-Harvey, Irene; Salminen, Juha-Pekka; Howlin, Brendan J; Frazier, Richard A

2014-09-17

Binding to bovine serum albumin of monomeric (vescalagin and pedunculagin) and dimeric ellagitannins (roburin A, oenothein B, and gemin A) was investigated by isothermal titration calorimetry and fluorescence spectroscopy, which indicated two types of binding sites. Stronger and more specific sites exhibited affinity constants, K1, of 10(4)-10(6) M(-1) and stoichiometries, n1, of 2-13 and dominated at low tannin concentrations. Weaker and less-specific binding sites had K2 constants of 10(3)-10(5) M(-1) and stoichiometries, n2, of 16-30 and dominated at higher tannin concentrations. Binding to stronger sites appeared to be dependent on tannin flexibility and the presence of free galloyl groups. Positive entropies for all but gemin A indicated that hydrophobic interactions dominated during complexation. This was supported by an exponential relationship between the affinity, K1, and the modeled hydrophobic accessible surface area and by a linear relationship between K1 and the Stern-Volmer quenching constant, K(SV).

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.

Effects of practice schedule and task specificity on the adaptive process of motor learning.

PubMed

Barros, João Augusto de Camargo; Tani, Go; Corrêa, Umberto Cesar

2017-10-01

This study investigated the effects of practice schedule and task specificity based on the perspective of adaptive process of motor learning. For this purpose, tasks with temporal and force control learning requirements were manipulated in experiments 1 and 2, respectively. Specifically, the task consisted of touching with the dominant hand the three sequential targets with specific movement time or force for each touch. Participants were children (N=120), both boys and girls, with an average age of 11.2years (SD=1.0). The design in both experiments involved four practice groups (constant, random, constant-random, and random-constant) and two phases (stabilisation and adaptation). The dependent variables included measures related to the task goal (accuracy and variability of error of the overall movement and force patterns) and movement pattern (macro- and microstructures). Results revealed a similar error of the overall patterns for all groups in both experiments and that they adapted themselves differently in terms of the macro- and microstructures of movement patterns. The study concludes that the effects of practice schedules on the adaptive process of motor learning were both general and specific to the task. That is, they were general to the task goal performance and specific regarding the movement pattern. Copyright © 2017 Elsevier B.V. All rights reserved.

The temperature dependence of the anisotropy constants for nickel

NASA Astrophysics Data System (ADS)

Szpunar, B.

1984-04-01

A universal function is suggested for the description of the temperature dependence of the anisotropy constants for Ni. The function has been obtained from the extended Stevens operators for J→ {1}/{2}. The prediction is in good agreement with experimental data.

Reproductive toxicity of monocrotophos to bobwhite quail

USGS Publications Warehouse

Stromborg, K.L.

1986-01-01

Pairs of 1st-year breeding bobwhites were fed constant or decreasing concentrations of monocrotophos for 15 days. In addition, a control diet was used in a pair-fed group matched with the pairs in the constant group. Dietary concentrations for the constant group were logarithmically spaced at .100, .178, .316, .562, 1.000 ppm of actual insecticide and also at 0 ppm (control) for five pairs at each concentration. The beginning concentrations for the decreasing pairs were identical to the constant group but regularly decreased to reach 25% of the starting concentrations by Day 13. Food consumption, egg production, hatchability of eggs under artificial incubation, and survival of hatched chicks for 2 weeks were recorded pairwise during 15-day treatment and 14-day posttreatment periods. Mortality was high at the greatest constant concentration and in the associated pair-fed group. Food consumption and egg production rates were negatively dose-related during the treatment period in the constant and decreasing groups. The laying rate of pair-fed hens was reduced to the same extent as in the constant group. Reproductive inhibition was not permanent, and pairs resumed laying after a dose-related recovery interval. No dose-related effects on hatchability or chick survival were detected. There was no evidence of a pesticide effect on reproduction other than that exerted through pesticide-induced anorexia.

Determination of Henry’s Law Constants Using Internal Standards with Benchmark Values

EPA Science Inventory

It is shown that Henry’s law constants can be experimentally determined by comparing headspace content of compounds with known constants to interpolate the constants of other compounds. Studies were conducted over a range of water temperatures to identify temperature dependence....

Scale Dependence of Dark Energy Antigravity

NASA Astrophysics Data System (ADS)

Perivolaropoulos, L.

2002-09-01

We investigate the effects of negative pressure induced by dark energy (cosmological constant or quintessence) on the dynamics at various astrophysical scales. Negative pressure induces a repulsive term (antigravity) in Newton's law which dominates on large scales. Assuming a value of the cosmological constant consistent with the recent SnIa data we determine the critical scale $r_c$ beyond which antigravity dominates the dynamics ($r_c \\sim 1Mpc $) and discuss some of the dynamical effects implied. We show that dynamically induced mass estimates on the scale of the Local Group and beyond are significantly modified due to negative pressure. We also briefly discuss possible dynamical tests (eg effects on local Hubble flow) that can be applied on relatively small scales (a few $Mpc$) to determine the density and equation of state of dark energy.

Unusual solvent effects on the fluorescence quenching rate constants of a thioxanthone derivative by n-butylamine and isoprene

NASA Astrophysics Data System (ADS)

Burget, D.; Jacques, P.

1998-07-01

The fluorescence quenching rate constants of a thioxanthone derivative by two electron donors ( n-butylamine and isoprene) were studied in eighteen solvents of different polarity. Both the empirical polarity parameter ET(30) and the more elaborate solvatochromic comparative method (SCM) π*, α, β (used without any precautions) failed to explain the relevant data. However, when in the frame of the SCM the sequential procedure is applied, unexpected solvent effects were revealed for hydroxylic solvents. These effects can be well accounted for by introducing a parameter χ for the whole set of solvents studied, equal to one or zero, depending on whether OH groups are involved or not in the quenching mechanism. A clue to the introduction of the parameter χ is presented.

Determination of acidity constants of curcumin in aqueous solution and apparent rate constant of its decomposition

NASA Astrophysics Data System (ADS)

Bernabé-Pineda, Margarita; Ramírez-Silva, María. Teresa; Romero-Romo, Mario; González-Vergara, Enrique; Rojas-Hernández, Alberto

2004-04-01

The stability of curcumin (H 3Cur) in aqueous media is improved when the systems in which it is present are at high pH values (higher than 11.7), fitting a model describable by a pseudo-zero order with a rate constant k' for the disappearance of the Cur 3- species of 1.39 (10 -9) M min -1. There were three acidity constants measured for the curcumin as follows: p KA3=10.51±0.01 corresponding to the equilibrium HCur 2-=Cur 3-+H +, a p KA2=9.88±0.02 corresponding to the equilibrium H 2Cur -=HCur -2+H +. These p KA values were attributed to the hydrogen of the phenol part of the curcumin, while the p KA1=8.38±0.04 corresponds to the equilibrium H 3Cur=H 2Cur -+H + and is attributed the acetylacetone type group. Formation of quinoid structures play an important role in the tautomeric forms of the curcumin in aqueous media, which makes the experimental values differ from the theoretically calculated ones, depending on the conditions adopted in the study.

Fluorescence properties of 3-amino phenylboronic acid and its interaction with glucose and ZnS:Cu quantum dots.

PubMed

Kur-Kowalska, Karolina; Przybyt, Małgorzata; Ziółczyk, Paulina; Sowiński, Przemysław; Miller, Ewa

2014-08-14

Preliminary results of a study of the interaction between 3-amino phenylboronic acid and glucose or ZnS:Cu quantum dots are presented in this paper. ZnS:Cu quantum dots with mercaptopropionic acid as a capping agent were obtained and characterized. Quenching of 3-amino phenylboronic acid fluorescence was studied by steady-state and timeresolved measurements. For fluorescence quenching with glucose the results of steady-state measurements fulfill Stern-Volmer equation. The quenching constants are increasing with growing pH. The decay of fluorescence is monoexponential with lifetime about 8.4 ns, which does not depend on pH and glucose concentration indicating static quenching. The quenching constant can be interpreted as apparent equilibrium constant of estrification of boronic group with diol. Quantum dots are also quenching 3-amino phenylboronic acid fluorescence. Fluorescence lifetime, in this case, is slightly decreasing with increasing concentration of quantum dots. The quenching constants are increasing slightly with pH's growth. Quenching mechanism of 3-amino phenylboronic acid fluorescence by quantum dots needs further experiments to be fully explained. Copyright © 2014 Elsevier B.V. All rights reserved.

Effects of movement and work load in patients with congenital central hypoventilation syndrome.

PubMed

Hager, Alfred; Koch, Walter; Stenzel, Heike; Hess, John; Schöber, Johannes

2007-04-01

Patients with congenital central hypoventilation syndrome lack ventilatory chemosensitivity and depend at least in part on the ergoreceptor function during exercise. In these patients a substantial increase of ventilation has been reported for passive movement during sleep as well as active movement on a treadmill. The aim of the study was to investigate ventilatory response to an increasing work load with constant movement. Eighteen patients and 17 healthy volunteers performed a cardiopulmonary exercise test on a bicycle pedaling at a constant rate of about 60 revolutions per minute throughout the entire test. The patients were able to exercise adequately and showed normal peak oxygen uptake. There was a steep rise in minute ventilation in both groups at the start of exercise, yet there was only a minor increase in both groups during the increase of workload up to the anaerobic threshold. After the anaerobic threshold, there was again an increase in ventilation in both groups, but the increase was less prominent in the patient group. Ventilation in patients with congenital central hypoventilation syndrome is increased during exercise caused both by movement (mechanoreceptors) and by anaerobic workload. This facilitates a normal ventilatory drive up to the anaerobic threshold and a normal exercise capacity in these patients.

Electronic Band Structure of Helical Polyisocyanides.

PubMed

Champagne, Benoît; Liégeois, Vincent; Fripiat, Joseph G; Harris, Frank E

2017-10-19

Restricted Hartree-Fock computations are reported for a methyl isocyanide polymer (repeating unit -C═N-CH 3 ), whose most stable conformation is expected to be a helical chain. The computations used a standard contracted Gaussian orbital set at the computational levels STO-3G, 3-21G, 6-31G, and 6-31G**, and studies were made for two line-group configurations motivated by earlier work and by studies of space-filling molecular models: (1) A structure of line-group symmetry L9 5 , containing a 9-fold screw axis with atoms displaced in the axial direction by 5/9 times the lattice constant, and (2) a structure of symmetry L4 1 that had been proposed, containing a 4-fold screw axis with translation by 1/4 of the lattice constant. Full use of the line-group symmetry was employed to cause most of the computational complexity to depend only on the size of the asymmetric repeating unit. Data reported include computed bond properties, atomic charge distribution, longitudinal polarizability, band structure, and the convoluted density of states. Most features of the description were found to be insensitive to the level of computational approximation. The work also illustrates the importance of exploiting line-group symmetry to extend the range of polymer structural problems that can be treated computationally.

Abiotic reduction of trifluralin and pendimethalin by sulfides in black-carbon-amended coastal sediments.

PubMed

Gong, Wenwen; Liu, Xinhui; Xia, Shuhua; Liang, Baocui; Zhang, Wei

2016-06-05

Dinitroaniline herbicides such as trifluralin and pendimethalin are persistent bioaccumulative toxins to aquatic organisms. Thus, in-situ remediation of contaminated sediments is desired. This study investigated whether black carbons (BCs), including apple wood charcoal (BC1), rice straw biochar (BC2), and activated carbon (BC3), could facilitate abiotic reduction of trifluralin and pendimethalin by sulfides of environmentally-relevant concentrations in anoxic coastal sediments. The reduction rates of trifluralin and pendimethalin increased substantially with increasing BC dosages in the sediments. This enhancing effect was dependent on BC type with the greatest for BC3 followed by BC1 and BC2, which well correlated with their specific surface area. The pseudo-first order reduction rate constants (kobs) for BC3-amended sediment (2%) were 13- and 14 times the rate constants in the BC-free sediment. The reduction rates increased with increasing temperature from 8 to 25°C in the BC-amended sediment, following the Arrhenius relationship. Finally, through molecular modeling by density functional theory and reaction species identification from mass spectra, molecular pathways of trifluralin and pendimethalin reduction were elucidated. In contrary to the separate sequential reduction of each nitro group to amine group, both nitro groups, first reduced to nitroso, then eventually to amine groups. Copyright © 2016 Elsevier B.V. All rights reserved.

Flow and volume dependence of rat airway resistance during constant flow inflation and deflation.

PubMed

Rubini, Alessandro; Carniel, Emanuele Luigi; Parmagnani, Andrea; Natali, Arturo Nicola

2011-12-01

The aim of this study was to measure the flow and volume dependence of both the ohmic and the viscoelastic pressure dissipations of the normal rat respiratory system separately during inflation and deflation. The study was conducted in the Respiratory Physiology Laboratory in our institution. Measurements were obtained for Seven albino Wistar rats of both sexes by using the flow interruption method during constant flow inflations and deflations. Measurements included anesthesia induction, tracheostomy and positioning of a tracheal cannula, positive pressure ventilation, constant flow respiratory system inflations and deflations at two different volumes and flows. The ohmic resistance exhibited volume and flow dependence, decreasing with lung volume and increasing with flow rate, during both inflation and deflation. The stress relaxation-related viscoelastic resistance also exhibited volume and flow dependence. It decreased with the flow rate at a constant lung volume during both inflation and deflation, but exhibited a different behavior with the lung volume at a constant flow rate (i.e., increased during inflations and decreased during deflations). Thus, stress relaxation in the rat lungs exhibited a hysteretic behavior. The observed flow and volume dependence of respiratory system resistance may be predicted by an equation derived from a model of the respiratory system that consists of two distinct compartments. The equation agrees well with the experimental data and indicates that the loading time is the critical parameter on which stress relaxation depends, during both lung inflation and deflation.

Context Dependent Effect of Landscape on the Occurrence of an Apex Predator across Different Climate Regions.

PubMed

Fujita, Go; Azuma, Atsuki; Nonaka, Jun; Sakai, Yoshiaki; Sakai, Hatsumi; Iseki, Fumitaka; Itaya, Hiroo; Fukasawa, Keita; Miyashita, Tadashi

2016-01-01

In studies of habitat suitability at landscape scales, transferability of species-landscape associations among sites are likely to be critical because it is often impractical to collect datasets across various regions. However, limiting factors, such as prey availability, are not likely to be constant across scales because of the differences in species pools. This is particularly true for top predators that are often the target for conservation concern. Here we focus on gray-faced buzzards, apex predators of farmland-dominated landscapes in East Asia. We investigated context dependency of "buzzard-landscape relationship", using nest location datasets from five sites, each differing in landscape composition. Based on the similarities of prey items and landscape compositions across the sites, we determined several alternative ways of grouping the sites, and then examined whether buzzard-landscape relationship change among groups, which was conducted separately for each way of grouping. As a result, the model of study-sites grouping based on similarities in prey items showed the smallest ΔAICc. Because the terms of interaction between group IDs and areas of broad-leaved forests and grasslands were selected, buzzard-landscape relationship showed a context dependency, i.e., these two landscape elements strengthen the relationship in southern region. The difference in prey fauna, which is associated with the difference in climate, might generate regional differences in the buzzard-landscape associations.

Shock tube measurements of growth constants in the branched chain formaldehyde-carbon monoxide-oxygen system

NASA Technical Reports Server (NTRS)

Brabbs, T. A.; Brokaw, R. S.

1982-01-01

Exponential free radical growth constants were measured for formaldehyde carbon monoxide-oxygen systems by monitoring the growth of oxygen atom concentration as manifested by CO flame band emission. Data were obtained over the temperature range of 1200 to 2000 K. The data were analyzed using a formaldehyde oxidation mechanism involving 12 elementary reaction steps. The computed growth constants are roughly in accord with experimental values, but are much more temperature dependent. The data was also analyzed assuming formaldehyde is rapidly decomposed to carbon monoxide and hydrogen. Growth constants computed for the resulting carbon monoxide hydrogen oxygen mixtures have a temperature dependence similar to experiments; however, for most mixtures, the computed growth constants were larger than experimental values.

Stepwise formation of H3O(+)(H2O)n in an ion drift tube: Empirical effective temperature of association/dissociation reaction equilibrium in an electric field.

PubMed

Nakai, Yoichi; Hidaka, Hiroshi; Watanabe, Naoki; Kojima, Takao M

2016-06-14

We measured equilibrium constants for H3O(+)(H2O)n-1 + H2O↔H3O(+)(H2O)n (n = 4-9) reactions taking place in an ion drift tube with various applied electric fields at gas temperatures of 238-330 K. The zero-field reaction equilibrium constants were determined by extrapolation of those obtained at non-zero electric fields. From the zero-field reaction equilibrium constants, the standard enthalpy and entropy changes, ΔHn,n-1 (0) and ΔSn,n-1 (0), of stepwise association for n = 4-8 were derived and were in reasonable agreement with those measured in previous studies. We also examined the electric field dependence of the reaction equilibrium constants at non-zero electric fields for n = 4-8. An effective temperature for the reaction equilibrium constants at non-zero electric field was empirically obtained using a parameter describing the electric field dependence of the reaction equilibrium constants. Furthermore, the size dependence of the parameter was thought to reflect the evolution of the hydrogen-bond structure of H3O(+)(H2O)n with the cluster size. The reflection of structural information in the electric field dependence of the reaction equilibria is particularly noteworthy.

Spinel-olivine-pryoxene equilibrium iron isotopic fractionation and applications to natural peridotites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Roskosz, Mathieu; Sio, Corliss K. I.; Dauphas, Nicolas

2015-11-15

Eight spinel-group minerals were synthesized by a flux-growth method producing spinels with varying composition and Fe3+/Fe-tot ratios. The mean force constants of iron bonds in these minerals were determined by synchrotron nuclear resonant inelastic X-ray scattering (NRIXS) in order to determine the reduced isotopic partition function ratios (beta-factors) of these spinels. The mean force constants are strongly dependent on the Fe3+/Fe-tot of the spinel but are independent, or weakly dependent on other structural and compositional parameters. From our spectroscopic data, it is found that a single redox-dependent calibration line accounts for the effects of Fe3+/Fe-tot on the beta-factors of spinels.more » This calibration successfully describes the equilibrium Fe isotopes fractionation factors between spinels and silicates (olivine and pyroxenes). Our predictions are in excellent agreement with independent determinations for the equilibrium Fe isotopic fractionations for the magnetite- fayalite and the magnetite-hedenbergite couples. Our calibration applies to the entire range of Fe3+/Fe-tot ratios found in natural spinels and provides a basis for interpreting iron isotopic variations documented in mantle peridotites. Except for a few exceptions, most of the samples measured so far are in isotopic disequilibrium, reflecting metasomatism and partial melting processes.« less

Mechanisms for the adsorption of substituted nitrobenzenes by smectite clays.

PubMed

Boyd, S A; Sheng, G; Teppen, B J; Johnston, C T

2001-11-01

To more fully understand the potential for transport of nitroaromatic compounds in soils and subsoils,the adsorption of a series of para- and meta-substituted nitrobenzenes (SNBs) by K-smectite clay was measured. Adsorption isotherms were fit to the Freundlich equation, and the resultant Freundlich adsorption coefficients (log(Kf) were positively correlated with the Hammett substituent constant (r2 = 0.80). This relationship and a positive reaction constant (p = 1.15) indicate that the adsorption reaction is favored by electron-withdrawing substituents. These results are consistent with an electron donor (smectite)-acceptor (substituted nitrobenzene) mechanism offered previously. However, quantum calculations did not reveal any systematic relationship between the Hammett constant and the electron density on the aromatic ring, which would explain a donor-acceptor relationship. Rather, electron density donated by a second substituent on nitrobenzene appears to be appropriated by the nitro group leaving ring electron density unchanged. Fourier transform infrared spectroscopy revealed shifts in the -NO2 vibrational modes of 1,3,5-trinitrobenzene (TNB) upon adsorption to K+-smectite that were consistent with the complexation of K+ by -NO2 groups. Such TNB vibrational shifts were not observed for SWy-1 saturated with more strongly hydrated cations (i.e., Na+, Mg2+, Ca2+, and Ba2+). The simultaneous interaction of multiple -NO2 groups with exchangeable K+ was indicated by molecular dynamic simulations. Adsorption of SNBs by smectite clays appears to result from the additive interactions of -NO2 groups and secondary substituents with interlayer K+ ions. Adsorption occurs to a greater or lesser extent depending on the abilities of substituents to complex additional interlayer cations and the water solubilities of SNBs. We conclude that the adsorption trends of SNBs on K-SAz-1 can be explained without recourse to hypothetical electron donor-acceptor complexes.

Defect-induced change of temperature-dependent elastic constants in BCC iron

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gao, N.; Setyawan, W.; Zhang, S. H.

2017-07-01

The effects of radiation-induced defects (randomly distributed vacancies, voids, and interstitial dislocation loops) on temperature-dependent elastic constants, C11, C12, and C44 in BCC iron, are studied with molecular dynamics method. The elastic constants are found to decrease with increasing temperatures for all cases containing different defects. The presence of vacancies, voids, or interstitial loops further decreases the elastic constants. For a given number of point defects, the randomly distributed vacancies show the strongest effect compared to voids or interstitial loops. All these results are expected to provide useful information to combine with experimental results for further understanding of radiation damage.

Temperature-dependent elastic stiffness constants of α- and θ-Al2O3 from first-principles calculations

NASA Astrophysics Data System (ADS)

Shang, Shun-Li; Zhang, Hui; Wang, Yi; Liu, Zi-Kui

2010-09-01

Temperature-dependent elastic stiffness constants (cijs), including both the isothermal and isoentropic ones, have been predicted for rhombohedral α-Al2O3 and monoclinic θ-Al2O3 in terms of a quasistatic approach, i.e., a combination of volume-dependent cijs determined by a first-principles strain versus stress method and direction-dependent thermal expansions obtained by first-principles phonon calculations. A good agreement is observed between the predictions and the available experiments for α-Al2O3, especially for the off-diagonal elastic constants. In addition, the temperature-dependent cijs predicted herein, in particular the ones for metastable θ-Al2O3, enable the stress analysis at elevated temperatures in thermally grown oxides containing α- and θ-Al2O3, which are crucial to understand the failure of thermal barrier coatings in gas-turbine engines.

Quantum Calculations on Salt Bridges with Water: Potentials, Structure, and Properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liao, Sing; Green, Michael E.

2011-01-01

Salt bridges are electrostatic links between acidic and basic amino acids in a protein; quantum calculations are used here to determine the energetics and other properties of one form of these species, in the presence of water molecules. The acidic groups are carboxylic acids (aspartic and glutamic acids); proteins have two bases with pK above physiological pH: one, arginine, with a guanidinium basic group, the other lysine, which is a primary amine. Only arginine is modeled here, by ethyl guanidinium, while propionic acid is used as a model for either carboxylic acid. The salt bridges are accompanied by 0-12 watermore » molecules; for each of the 13 systems, the energy-bond distance relation, natural bond orbitals (NBO), frequency calculations allowing thermodynamic corrections to room temperature, and dielectric constant dependence, were all calculated. The water molecules were found to arrange themselves in hydrogen bonded rings anchored to the oxygens of the salt bridge components. This was not surprising in itself, but it was found that the rings lead to a periodicity in the energy, and to a 'water addition' rule. The latter shows that the initial rings, with four oxygen atoms, become five member rings when an additional water molecule becomes available, with the additional water filling in at the bond with the lowest Wiberg index, as calculated using NBO. The dielectric constant dependence is the expected hyperbola, and the fit of the energy to the inverse dielectric constant is determined. There is an energy periodicity related to ring formation upon addition of water molecules. When 10 water molecules have been added, all spaces near the salt bridge are filled, completing the first hydration shell, and a second shell starts to form. The potentials associated with salt bridges depend on their hydration, and potentials assigned without regard to local hydration are likely to cause errors as large as or larger than kBT, thus suggesting a serious problem if these potentials are used in Molecular Dynamics simulations.« less

Reaction of SO2 with OH in the atmosphere.

PubMed

Long, Bo; Bao, Junwei Lucas; Truhlar, Donald G

2017-03-15

The OH + SO 2 reaction plays a critical role in understanding the oxidation of SO 2 in the atmosphere, and its rate constant is critical for clarifying the fate of SO 2 in the atmosphere. The rate constant of the OH + SO 2 reaction is calculated here by using beyond-CCSDT correlation energy calculations for a benchmark, validated density functional methods for direct dynamics, canonical variational transition state theory with anharmonicity and multidimensional tunneling for the high-pressure rate constant, and system-specific quantum RRK theory for pressure effects; the combination of these methods can compete in accuracy with experiments. There has been a long-term debate in the literature about whether the OH + SO 2 reaction is barrierless, but our calculations indicate a positive barrier with an transition structure that has an enthalpy of activation of 0.27 kcal mol -1 at 0 K. Our results show that the high-pressure limiting rate constant of the OH + SO 2 reaction has a positive temperature dependence, but the rate constant at low pressures has a negative temperature dependence. The computed high-pressure limiting rate constant at 298 K is 1.25 × 10 -12 cm 3 molecule -1 s -1 , which agrees excellently with the value (1.3 × 10 -12 cm 3 molecule -1 s -1 ) recommended in the most recent comprehensive evaluation for atmospheric chemistry. We show that the atmospheric lifetime of SO 2 with respect to oxidation by OH depends strongly on altitude (in the range 0-50 km) due to the falloff effect. We introduce a new interpolation procedure for fitting the combined temperature and pressure dependence of the rate constant, and it fits the calculated rate constants over the whole range with a mean unsigned error of only 7%. The present results provide reliable kinetics data for this specific reaction, and also they demonstrate convenient theoretical methods that can be reliable for predicting rate constants of other gas-phase reactions.

Estimation of the engineering elastic constants of a directionally solidified superalloy for finite element structural analysis

NASA Technical Reports Server (NTRS)

Abdul-Aziz, Ali; Kalluri, Sreeramesh

1991-01-01

The temperature-dependent engineering elastic constants of a directionally solidified nickel-base superalloy were estimated from the single-crystal elastic constants of nickel and MAR-MOO2 superalloy by using Wells' method. In this method, the directionally solidified (columnar-grained) nickel-base superalloy was modeled as a transversely isotropic material, and the five independent elastic constants of the transversely isotropic material were determined from the three independent elastic constants of a cubic single crystal. Solidification for both the single crystals and the directionally solidified superalloy was assumed to be along the (001) direction. Temperature-dependent Young's moduli in longitudinal and transverse directions, shear moduli, and Poisson's ratios were tabulated for the directionally solidified nickel-base superalloy. These engineering elastic constants could be used as input for performing finite element structural analysis of directionally solidified turbine engine components.

Experience-Dependent Color Constancy in Guppies (Poecilia reticulata)

PubMed Central

Intskirveli, I. E.; Roinishvili, M. O.; Kezeli, A. R.

2002-01-01

We investigated the ability to recognize the color of surfaces in fish (Poecilia reticulata), bred from birth in conditions of artificial light with constant spectral content. The capacity for color constancy significantly deteriorated when compared that to the control group. Further alteration of lighting conditions and transfer into natural daylight conditions restored the suppressed function to its normal level. We suggest that the color constancy function belongs in the visual system-response functions, the full development of which requires the accumulation of individual visual experience. PMID:12757371

Experience-dependent color constancy in guppies (Poecilia reticulata).

PubMed

Intskirveli, I E; Roinishvili, M O; Kezeli, A R

2002-01-01

We investigated the ability to recognize the color of surfaces in fish (Poecilia reticulata), bred from birth in conditions of artificial light with constant spectral content. The capacity for color constancy significantly deteriorated when compared that to the control group. Further alteration of lighting conditions and transfer into natural daylight conditions restored the suppressed function to its normal level. We suggest that the color constancy function belongs in the visual system-response functions, the full development of which requires the accumulation of individual visual experience.

Species-Specific Thiol-Disulfide Equilibrium Constant: A Tool To Characterize Redox Transitions of Biological Importance.

PubMed

Mirzahosseini, Arash; Somlyay, Máté; Noszál, Béla

2015-08-13

Microscopic redox equilibrium constants, a new species-specific type of physicochemical parameters, were introduced and determined to quantify thiol-disulfide equilibria of biological significance. The thiol-disulfide redox equilibria of glutathione with cysteamine, cysteine, and homocysteine were approached from both sides, and the equilibrium mixtures were analyzed by quantitative NMR methods to characterize the highly composite, co-dependent acid-base and redox equilibria. The directly obtained, pH-dependent, conditional constants were then decomposed by a new evaluation method, resulting in pH-independent, microscopic redox equilibrium constants for the first time. The 80 different, microscopic redox equilibrium constant values show close correlation with the respective thiolate basicities and provide sound means for the development of potent agents against oxidative stress.

Inflation with a smooth constant-roll to constant-roll era transition

NASA Astrophysics Data System (ADS)

Odintsov, S. D.; Oikonomou, V. K.

2017-07-01

In this paper, we study canonical scalar field models, with a varying second slow-roll parameter, that allow transitions between constant-roll eras. In the models with two constant-roll eras, it is possible to avoid fine-tunings in the initial conditions of the scalar field. We mainly focus on the stability of the resulting solutions, and we also investigate if these solutions are attractors of the cosmological system. We shall calculate the resulting scalar potential and, by using a numerical approach, we examine the stability and attractor properties of the solutions. As we show, the first constant-roll era is dynamically unstable towards linear perturbations, and the cosmological system is driven by the attractor solution to the final constant-roll era. As we demonstrate, it is possible to have a nearly scale-invariant power spectrum of primordial curvature perturbations in some cases; however, this is strongly model dependent and depends on the rate of the final constant-roll era. Finally, we present, in brief, the essential features of a model that allows oscillations between constant-roll eras.

The influence of polarizability and charge transfer on specific ion effects in the dynamics of aqueous salt solutions

NASA Astrophysics Data System (ADS)

Nguyen, Mary; Rick, Steven W.

2018-06-01

The diffusion rates for water molecules in salt solutions depend on the identity of the ions, as well as their concentration. Among the alkali metal ions, cesium and potassium increase and sodium strongly decreases the diffusion constant of water. The origin of the difference can be understood by examining the simulation results using different potential models. In this work, aqueous solutions of salts are simulated with a variety of models. Commonly used non-polarizable models, which otherwise reproduce many experimental properties, do not capture the trend in the diffusion constant, while models which include polarization and/or charge transfer interactions do. For the non-polarizable models, the diffusion constant decreases too strongly with salt concentration. The changes in the water diffusion constant with increasing salt concentration match the diffusion constant of the ion. The ion diffusion constant is dependent on the residence time for water in the ion solvation shell. The non-polarizable models over-estimate the residence time, relative to the translational diffusion constant and so tend to under-estimate the ion and water diffusion constants.

Spectrofluorimetric determination of stoichiometry and association constants of the complexes of harmane and harmine with beta-cyclodextrin and chemically modified beta-cyclodextrins.

PubMed

Martín, L; León, A; Olives, A I; Del Castillo, B; Martín, M A

2003-06-13

The association characteristics of the inclusion complexes of the beta-carboline alkaloids harmane and harmine with beta-cyclodextrin (beta-CD) and chemically modified beta-cyclodextrins such as hydroxypropyl-beta-cyclodextrin (HPbeta-CD), 2,3-di-O-methyl-beta-cyclodextrin (DMbeta-CD) and 2,3,6-tri-O-methyl-beta-cyclodextrin (TMbeta-CD) are described. The association constants vary from 112 for harmine/DMbeta-CD to 418 for harmane/HPbeta-CD. The magnitude of the interactions between the host and the guest molecules depends on the chemical and geometrical characteristics of the guest molecules and therefore the association constants vary for the different cyclodextrin complexes. The steric hindrance is higher in the case of harmine due to the presence of methoxy group on the beta-carboline ring. The association obtained for the harmane complexes is stronger than the one observed for harmine complexes except in the case of harmine/TMbeta-CD. Important differences in the association constants were observed depending on the experimental variable used in the calculations (absolute value of fluorescence intensity or the ratio between the fluorescence intensities corresponding to the neutral and cationic forms). When fluorescence intensity values were considered, the association constants were higher than when the ratio of the emission intensity for the cationic and neutral species was used. These differences are a consequence of the co-existence of acid-base equilibria in the ground and in excited states together with the complexation equilibria. The existence of a proton transfer reaction in the excited states of harmane or harmine implies the need for the experimental dialysis procedure for separation of the complexes from free harmane or harmine. Such methodology allows quantitative results for stoichiometry determinations to be obtained, which show the existence of both 1:1 and 1:2 beta-carboline alkaloid:CD complexes with different solubility properties.

Dissociation between implicit and explicit responses in postconditioning UCS revaluation after fear conditioning in humans

PubMed Central

Schultz, Douglas H.; Balderston, Nicholas L.; Geiger, Jennifer A.; Helmstetter, Fred J.

2014-01-01

The nature of the relationship between explicit and implicit learning is a topic of considerable debate. In order to investigate this relationship we conducted two experiments on postconditioning revaluation of the unconditional stimulus (UCS) in human fear conditioning. In Experiment 1, the intensity of the UCS was decreased following acquisition for one group (devaluation) and held constant for another group (control). A subsequent test revealed that even though both groups exhibited similar levels of UCS expectancy, the devaluation group had significantly smaller conditional skin conductance responses. The devaluation effect was not explained by differences in the explicit estimates of UCS probability or explicit knowledge that the UCS intensity had changed. In Experiment 2, the value of the UCS was increased following acquisition for one group (inflation) and held constant for another group (control). Test performance revealed that UCS inflation did not alter expectancy ratings, but the inflation group exhibited larger learned skin conductance responses than the control group. The inflation effect was not explained by differences in the explicit estimates of UCS probability or explicit knowledge that the UCS intensity had changed. The SCR revaluation effect was not dependent on explicit memory processes in either experiment. In both experiments we found differences on an implicit measure of learning in the absence of changes in explicit measures. Together, the differences observed between expectancy measures and skin conductance support the idea that these responses might reflect different types of memory formed during the same training procedure and be supported by separate neural systems. PMID:23731073

Profiles of equilibrium constants for self-association of aromatic molecules

NASA Astrophysics Data System (ADS)

Beshnova, Daria A.; Lantushenko, Anastasia O.; Davies, David B.; Evstigneev, Maxim P.

2009-04-01

Analysis of the noncovalent, noncooperative self-association of identical aromatic molecules assumes that the equilibrium self-association constants are either independent of the number of molecules (the EK-model) or change progressively with increasing aggregation (the AK-model). The dependence of the self-association constant on the number of molecules in the aggregate (i.e., the profile of the equilibrium constant) was empirically derived in the AK-model but, in order to provide some physical understanding of the profile, it is proposed that the sources for attenuation of the equilibrium constant are the loss of translational and rotational degrees of freedom, the ordering of molecules in the aggregates and the electrostatic contribution (for charged units). Expressions are derived for the profiles of the equilibrium constants for both neutral and charged molecules. Although the EK-model has been widely used in the analysis of experimental data, it is shown in this work that the derived equilibrium constant, KEK, depends on the concentration range used and hence, on the experimental method employed. The relationship has also been demonstrated between the equilibrium constant KEK and the real dimerization constant, KD, which shows that the value of KEK is always lower than KD.

Backstepping-based boundary control design for a fractional reaction diffusion system with a space-dependent diffusion coefficient.

PubMed

Chen, Juan; Cui, Baotong; Chen, YangQuan

2018-06-11

This paper presents a boundary feedback control design for a fractional reaction diffusion (FRD) system with a space-dependent (non-constant) diffusion coefficient via the backstepping method. The contribution of this paper is to generalize the results of backstepping-based boundary feedback control for a FRD system with a space-independent (constant) diffusion coefficient to the case of space-dependent diffusivity. For the boundary stabilization problem of this case, a designed integral transformation treats it as a problem of solving a hyperbolic partial differential equation (PDE) of transformation's kernel, then the well posedness of the kernel PDE is solved for the plant with non-constant diffusivity. Furthermore, by the fractional Lyapunov stability (Mittag-Leffler stability) theory and the backstepping-based boundary feedback controller, the Mittag-Leffler stability of the closed-loop FRD system with non-constant diffusivity is proved. Finally, an extensive numerical example for this closed-loop FRD system with non-constant diffusivity is presented to verify the effectiveness of our proposed controller. Copyright © 2018 ISA. Published by Elsevier Ltd. All rights reserved.

Preparation, structural and dielectric characteristics of Y0.5La0.95PO4 nanoparticles

NASA Astrophysics Data System (ADS)

Raina, Bindu; Verma, Seema; Gupta, Vandana; Bamzai, K. K.

2018-05-01

Nanoparticles of yttrium substituted lanthanum phosphate having formulae Y0.5La0.95PO4 were successfully prepared through co-precipitation method. The phase, purity and crystallinity of 5% yttrium substituted lanthanum phosphate (Y: LaP 5%) powder was characterized by X-ray diffraction technique which suggests the sample belonging to monoclinic monazite crystal system. The spherical morphology with partial agglomeration having grain size in the nano scale range was observed with transmission electron microscopy. FTIR analysis depicts the presence of water molecule along with the phosphate group. The electrical properties of the grown composition show dependence of dielectric constant and dielectric loss on frequency and temperature. The continuous decrease in dielectric constant with increase in frequency suggests that the conduction mechanism is due to hopping of the charge carriers from one site to another.

Dynamics in a ratio-dependent predator-prey model with predator harvesting

NASA Astrophysics Data System (ADS)

Xiao, Dongmei; Li, Wenxia; Han, Maoan

2006-12-01

The objective of this paper is to study systematically the dynamical properties of a ratio-dependent predator-prey model with nonzero constant rate predator harvesting. It is shown that the model has at most two equilibria in the first quadrant and can exhibit numerous kinds of bifurcation phenomena, including the bifurcation of cusp type of codimension 2 (i.e., Bogdanov-Takens bifurcation), the subcritical and supercritical Hopf bifurcations. These results reveal far richer dynamics compared to the model with no harvesting and different dynamics compared to the model with nonzero constant rate prey harvesting in [D. Xiao, L. Jennings, Bifurcations of a ratio-dependent predator-prey system with constant rate harvesting, SIAM Appl. Math. 65 (2005) 737-753]. Biologically, it is shown that nonzero constant rate predator harvesting can prevent mutual extinction as a possible outcome of the predator prey interaction, and remove the singularity of the origin, which was regarded as "pathological behavior" for a ratio-dependent predator prey model in [P. Yodzis, Predator-prey theory and management of multispecies fisheries, Ecological Applications 4 (2004) 51-58].

Tolman lengths and rigidity constants of multicomponent fluids: Fundamental theory and numerical examples

NASA Astrophysics Data System (ADS)

Aasen, Ailo; Blokhuis, Edgar M.; Wilhelmsen, Øivind

2018-05-01

The curvature dependence of the surface tension can be described by the Tolman length (first-order correction) and the rigidity constants (second-order corrections) through the Helfrich expansion. We present and explain the general theory for this dependence for multicomponent fluids and calculate the Tolman length and rigidity constants for a hexane-heptane mixture by use of square gradient theory. We show that the Tolman length of multicomponent fluids is independent of the choice of dividing surface and present simple formulae that capture the change in the rigidity constants for different choices of dividing surface. For multicomponent fluids, the Tolman length, the rigidity constants, and the accuracy of the Helfrich expansion depend on the choice of path in composition and pressure space along which droplets and bubbles are considered. For the hexane-heptane mixture, we find that the most accurate choice of path is the direction of constant liquid-phase composition. For this path, the Tolman length and rigidity constants are nearly linear in the mole fraction of the liquid phase, and the Helfrich expansion represents the surface tension of hexane-heptane droplets and bubbles within 0.1% down to radii of 3 nm. The presented framework is applicable to a wide range of fluid mixtures and can be used to accurately represent the surface tension of nanoscopic bubbles and droplets.

Hydroxylation of p-substituted phenols by tyrosinase: Further insight into the mechanism of tyrosinase activity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Munoz-Munoz, Jose Luis; Berna, Jose; Garcia-Molina, Maria del Mar

2012-07-27

Highlights: Black-Right-Pointing-Pointer The action the copper complexes and tyrosinase on phenols is equivalent. Black-Right-Pointing-Pointer Isotope effect showed that nucleophilic attack to copper atom may be the slower step. Black-Right-Pointing-Pointer The value of {rho} (Hammett constant) supports an electrophilic aromatic substitution. Black-Right-Pointing-Pointer Data obtained in steady state pH 7 conditions support the mechanism of Scheme 1SM. -- Abstract: A study of the monophenolase activity of tyrosinase by measuring the steady state rate with a group of p-substituted monophenols provides the following kinetic information: k{sub cat}{sup m} and the Michaelis constant, K{sub M}{sup m}. Analysis of these data taking into account chemicalmore » shifts of the carbon atom supporting the hydroxyl group ({delta}) and {sigma}{sub p}{sup +}, enables a mechanism to be proposed for the transformation of monophenols into o-diphenols, in which the first step is a nucleophilic attack on the copper atom on the form E{sub ox} (attack of the oxygen of the hydroxyl group of C-1 on the copper atom) followed by an electrophilic attack (attack of the hydroperoxide group on the ortho position with respect to the hydroxyl group of the benzene ring, electrophilic aromatic substitution with a reaction constant {rho} of -1.75). These steps show the same dependency on the electronic effect of the substituent groups in C-4. Furthermore, a study of a solvent deuterium isotope effect on the oxidation of monophenols by tyrosinase points to an appreciable isotopic effect. In a proton inventory study with a series of p-substituted phenols, the representation of k{sub cat}{sup f{sub n}}/k{sub cat}{sup f{sub 0}} against n (atom fractions of deuterium), where k{sub cat}{sup f{sub n}} is the catalytic constant for a molar fraction of deuterium (n) and k{sub cat}{sup f{sub 0}} is the corresponding kinetic parameter in a water solution, was linear for all substrates. These results indicate that only one of the proton transfer processes from the hydroxyl groups involved the catalytic cycle is responsible for the isotope effects. We suggest that this step is the proton transfer from the hydroxyl group of C-1 to the peroxide of the oxytyrosinase form (E{sub ox}). After the nucleophilic attack, the incorporation of the oxygen in the benzene ring occurs by means of an electrophilic aromatic substitution mechanism in which there is no isotopic effect.« less

Improved resolution of single channel dwell times reveals mechanisms of binding, priming, and gating in muscle AChR

PubMed Central

Mukhtasimova, Nuriya; daCosta, Corrie J.B.

2016-01-01

The acetylcholine receptor (AChR) from vertebrate skeletal muscle initiates voluntary movement, and its kinetics of activation are crucial for maintaining the safety margin for neuromuscular transmission. Furthermore, the kinetic mechanism of the muscle AChR serves as an archetype for understanding activation mechanisms of related receptors from the Cys-loop superfamily. Here we record currents through single muscle AChR channels with improved temporal resolution approaching half an order of magnitude over our previous best. A range of concentrations of full and partial agonists are used to elicit currents from human wild-type and gain-of-function mutant AChRs. For each agonist–receptor combination, rate constants are estimated from maximum likelihood analysis using a kinetic scheme comprised of agonist binding, priming, and channel gating steps. The kinetic scheme and rate constants are tested by stochastic simulation, followed by incorporation of the experimental step response, sampling rate, background noise, and filter bandwidth. Analyses of the simulated data confirm all rate constants except those for channel gating, which are overestimated because of the established effect of noise on the briefest dwell times. Estimates of the gating rate constants were obtained through iterative simulation followed by kinetic fitting. The results reveal that the agonist association rate constants are independent of agonist occupancy but depend on receptor state, whereas those for agonist dissociation depend on occupancy but not on state. The priming rate and equilibrium constants increase with successive agonist occupancy, and for a full agonist, the forward rate constant increases more than the equilibrium constant; for a partial agonist, the forward rate and equilibrium constants increase equally. The gating rate and equilibrium constants also increase with successive agonist occupancy, but unlike priming, the equilibrium constants increase more than the forward rate constants. As observed for a full and a partial agonist, the gain-of-function mutation affects the relationship between rate and equilibrium constants for priming but not for channel gating. Thus, resolving brief single channel currents distinguishes priming from gating steps and reveals how the corresponding rate and equilibrium constants depend on agonist occupancy. PMID:27353445

Investigation and kinetic evaluation of the reactions of hydroxymethylfurfural with amino and thiol groups of amino acids.

PubMed

Hamzalıoğlu, Aytül; Gökmen, Vural

2018-02-01

In this study, reactions of hydroxymethylfurfural (HMF) with selected amino acids (arginine, cysteine and lysine) were investigated in HMF-amino acid (high moisture) and Coffee-amino acid (low moisture) model systems at 5, 25 and 50°C. The results revealed that HMF reacted efficiently and effectively with amino acids in both high and low moisture model systems. High-resolution mass spectrometry (HRMS) analyses of the reaction mixtures confirmed the formations of Michael adduct and Schiff base of HMF with amino acids. Calculated pseudo-first order reaction rate constants were in the following order; k Cysteine >k Arginine >k Lysine for high moisture model systems. Comparing to these rate constants, the k Cysteine decreased whereas, k Arginine and k Lysine increased under the low moisture conditions of Coffee-amino acid model systems. The temperature dependence of the rate constants was found to obey the Arrhenius law in a temperature range of 5-50°C under both low and high moisture conditions. Copyright © 2017 Elsevier Ltd. All rights reserved.

Output characteristics of SASE-driven short wavelength FEL`s

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fawley, W.M.

This paper investigates various properties of the ``microspikes`` associated with self-amplified spontaneous emission (SASE) in a short wavelength free-electron laser (FEL). Using results from the 2-D numerical simulation code GINGER, we confirm theoretical predictions such as the convective group velocity in the exponential gain regime. In the saturated gain regime beyond the initial saturation, we find that the average radiation power continues to grow with an approximately linearly dependence upon undulator length. Moreover, the spectrum significantly broadens and shifts in wavelength to the redward direction, with{ital P(w)} approaching a constant, asymptotic value. This is in marked contrast to the exponentialmore » gain regime where the spectrum steadily narrows, {ital P(w)} grows, and the central wavelength remains constant with {ital z}. Via use of a spectrogram diagnostic {ital S(w,t)}, it appears that the radiation pattern in the saturated gain regime is composed of an ensemble of distinct ``sinews`` whose widths AA remain approximately constant but whose central wavelengths can ``chirp`` by varying a small extent with {ital t}.« less

Effects of the rate of formant-frequency variation on the grouping of formants in speech perception.

PubMed

Summers, Robert J; Bailey, Peter J; Roberts, Brian

2012-04-01

How speech is separated perceptually from other speech remains poorly understood. Recent research suggests that the ability of an extraneous formant to impair intelligibility depends on the modulation of its frequency, but not its amplitude, contour. This study further examined the effect of formant-frequency variation on intelligibility by manipulating the rate of formant-frequency change. Target sentences were synthetic three-formant (F1 + F2 + F3) analogues of natural utterances. Perceptual organization was probed by presenting stimuli dichotically (F1 + F2C + F3C; F2 + F3), where F2C + F3C constitute a competitor for F2 and F3 that listeners must reject to optimize recognition. Competitors were derived using formant-frequency contours extracted from extended passages spoken by the same talker and processed to alter the rate of formant-frequency variation, such that rate scale factors relative to the target sentences were 0, 0.25, 0.5, 1, 2, and 4 (0 = constant frequencies). Competitor amplitude contours were either constant, or time-reversed and rate-adjusted in parallel with the frequency contour. Adding a competitor typically reduced intelligibility; this reduction increased with competitor rate until the rate was at least twice that of the target sentences. Similarity in the results for the two amplitude conditions confirmed that formant amplitude contours do not influence across-formant grouping. The findings indicate that competitor efficacy is not tuned to the rate of the target sentences; most probably, it depends primarily on the overall rate of frequency variation in the competitor formants. This suggests that, when segregating the speech of concurrent talkers, differences in speech rate may not be a significant cue for across-frequency grouping of formants.

Dynamics and structure of hydrogen-bonding glass formers: Comparison between hexanetriol and sugar alcohols based on dielectric relaxation

NASA Astrophysics Data System (ADS)

Nakanishi, Masahiro; Nozaki, Ryusuke

2010-04-01

Broadband dielectric spectra of supercooled 1,2,6-hexanetriol are presented in order to reveal physical picture behind a glass transition of polyhydric alcohols. It has been reported so far that temperature dependences of α relaxation time for sugar alcohols exhibit systematic trend against number of carbon atoms or OH groups per molecule. However, because each molecule is composed of equal number of carbon atoms and OH groups in the case of the reported sugar alcohols, the more dominant parameter to govern the α relaxation dynamics has not been discussed. By using a chemical structure of the hexanetriol composed of the deferent number of carbon and OH, it is possible to determine the dominant parameter. From temperature dependence of α relaxation times, it is strongly supported that the number of OH groups is the dominant parameter. Furthermore, from an analysis of static dielectric constant, it is suggested that local hydrogen-bonding structure is similar among all polyhydric alcohols. From these two results, a simple picture of the origin of the systematic character is proposed.

Dynamics and structure of hydrogen-bonding glass formers: comparison between hexanetriol and sugar alcohols based on dielectric relaxation.

PubMed

Nakanishi, Masahiro; Nozaki, Ryusuke

2010-04-01

Broadband dielectric spectra of supercooled 1,2,6-hexanetriol are presented in order to reveal physical picture behind a glass transition of polyhydric alcohols. It has been reported so far that temperature dependences of alpha relaxation time for sugar alcohols exhibit systematic trend against number of carbon atoms or OH groups per molecule. However, because each molecule is composed of equal number of carbon atoms and OH groups in the case of the reported sugar alcohols, the more dominant parameter to govern the alpha relaxation dynamics has not been discussed. By using a chemical structure of the hexanetriol composed of the deferent number of carbon and OH, it is possible to determine the dominant parameter. From temperature dependence of alpha relaxation times, it is strongly supported that the number of OH groups is the dominant parameter. Furthermore, from an analysis of static dielectric constant, it is suggested that local hydrogen-bonding structure is similar among all polyhydric alcohols. From these two results, a simple picture of the origin of the systematic character is proposed.

Developmental plasticity of growth and digestive efficiency in dependence of early-life food availability

PubMed Central

Kotrschal, Alexander; Szidat, Sönke; Taborsky, Barbara

2014-01-01

Nutrition is a potent mediator of developmental plasticity. If food is scarce, developing organisms may invest into growth to outgrow size-dependent mortality (short-term benefit) and/or into an efficient digestion system (long-term benefit). We investigated this potential trade-off, by determining the influence of food availability on juvenile body and organ growth, and on adult digestive efficiency in the cichlid fish Simochromis pleurospilus. We reared two groups of fish at constant high or low food rations, and we switched four other groups between these two rations at an early and late juvenile period. We measured juvenile growth and organ sizes at different developmental stages and determined adult digestive efficiency. Fish kept at constant, high rations grew considerably faster than low-food fish. Nevertheless, S. pleurospilus partly buffered the negative effects of low food availability by developing heavier digestive organs, and they were therefore more efficient in digesting their food as adults. Results of fish exposed to a ration switch during either the early or late juvenile period suggest (i) that the ability to show compensatory growth after early exposure to low food availability persists during the juvenile period, (ii) that digestive efficiency is influenced by varying juvenile food availability during the late juvenile phase and (iii) that the efficiency of the adult digestive system is correlated with the growth rate during a narrow time window of juvenile period. PMID:25866430

High-Throughput Screening of Sulfide Thermoelectric Materials Using Electron Transport Calculations with OpenMX and BoltzTraP

NASA Astrophysics Data System (ADS)

Miyata, Masanobu; Ozaki, Taisuke; Takeuchi, Tsunehiro; Nishino, Shunsuke; Inukai, Manabu; Koyano, Mikio

2018-06-01

The electron transport properties of 809 sulfides have been investigated using density functional theory (DFT) calculations in the relaxation time approximation, and a material design rule established for high-performance sulfide thermoelectric (TE) materials. Benchmark electron transport calculations were performed for Cu12Sb4S13 and Cu26V2Ge6S32, revealing that the ratio of the scattering probability of electrons and phonons ( κ lat τ el -1 ) was constant at about 2 × 1014 W K-1 m-1 s-1. The calculated thermopower S dependence of the theoretical dimensionless figure of merit ZT DFT of the 809 sulfides showed a maximum at 140 μV K-1 to 170 μV K-1. Under the assumption of constant κ lat τ el -1 of 2 × 1014 W K-1 m-1 s-1 and constant group velocity v of electrons, a slope of the density of states of 8.6 states eV-2 to 10 states eV-2 is suitable for high- ZT sulfide TE materials. The Lorenz number L dependence of ZT DFT for the 809 sulfides showed a maximum at L of approximately 2.45 × 10-8 V2 K-2. This result demonstrates that the potential of high- ZT sulfide materials is highest when the electron thermal conductivity κ el of the symmetric band is equal to that of the asymmetric band.

Thickness Dependence of the Dzyaloshinskii-Moriya Interaction in Co2 FeAl Ultrathin Films: Effects of Annealing Temperature and Heavy-Metal Material

NASA Astrophysics Data System (ADS)

Belmeguenai, M.; Roussigné, Y.; Bouloussa, H.; Chérif, S. M.; Stashkevich, A.; Nasui, M.; Gabor, M. S.; Mora-Hernández, A.; Nicholson, B.; Inyang, O.-O.; Hindmarch, A. T.; Bouchenoire, L.

2018-04-01

The interfacial Dzyaloshinskii-Moriya interaction (IDMI) is investigated in Co2FeAl (CFA) ultrathin films of various thicknesses (0.8 nm ≤tCFA≤2 nm ) grown by sputtering on Si substrates, using Pt, W, Ir, and MgO buffer or/and capping layers. Vibrating sample magnetometry reveals that the magnetization at saturation (Ms ) for the Pt- and Ir-buffered films is higher than the usual Ms of CFA due to the proximity-induced magnetization (PIM) in Ir and Pt estimated to be 19% and 27%, respectively. The presence of PIM in these materials is confirmed using x-ray resonant magnetic reflectivity. Moreover, while no PIM is induced in W, higher PIM is obtained with Pt when it is used as a buffer layer rather than a capping layer. Brillouin light scattering in the Damon-Eshbach geometry is used to investigate the thickness dependences of the IDMI constants from the spin-wave nonreciprocity and the perpendicular anisotropy field versus the annealing temperature. The IDMI sign is found to be negative for Pt /CFA and Ir /CFA , while it is positive for W /CFA . The thickness dependence of the effective IDMI constant for stacks involving Pt and W shows the existence of two regimes similar to that of the perpendicular anisotropy constant due to the degradation of the interfaces as the CFA thickness approaches a critical thickness. The surface IDMI and anisotropy constants of each stack are determined for the thickest samples where a linear thickness dependence of the effective IDMI constant and the effective magnetization are observed. The interface anisotropy and IDMI constants investigated for the Pt /CFA /MgO system show different trends with the annealing temperature. The decrease of the IDMI constant with increasing annealing temperature is probably due to the electronic structure changes at the interfaces, while the increase of the interface anisotropy constant is coherent with the interface quality and disorder enhancement.

Spherical type integrable classical systems in a magnetic field

NASA Astrophysics Data System (ADS)

Marchesiello, A.; Šnobl, L.; Winternitz, P.

2018-04-01

We show that four classes of second order spherical type integrable classical systems in a magnetic field exist in the Euclidean space {E}3 , and construct the Hamiltonian and two second order integrals of motion in involution for each of them. For one of the classes the Hamiltonian depends on four arbitrary functions of one variable. This class contains the magnetic monopole as a special case. Two further classes have Hamiltonians depending on one arbitrary function of one variable and four or six constants, respectively. The magnetic field in these cases is radial. The remaining system corresponds to a constant magnetic field and the Hamiltonian depends on two constants. Questions of superintegrability—i.e. the existence of further integrals—are discussed.

Application of the compensated Arrhenius formalism to self-diffusion: implications for ionic conductivity and dielectric relaxation.

PubMed

Petrowsky, Matt; Frech, Roger

2010-07-08

Self-diffusion coefficients are measured from -5 to 80 degrees C in a series of linear alcohols using pulsed field gradient NMR. The temperature dependence of these data is studied using a compensated Arrhenius formalism that assumes an Arrhenius-like expression for the diffusion coefficient; however, this expression includes a dielectric constant dependence in the exponential prefactor. Scaling temperature-dependent diffusion coefficients to isothermal diffusion coefficients so that the exponential prefactors cancel results in calculated energies of activation E(a). The exponential prefactor is determined by dividing the temperature-dependent diffusion coefficients by the Boltzmann term exp(-E(a)/RT). Plotting the prefactors versus the dielectric constant places the data on a single master curve. This procedure is identical to that previously used to study the temperature dependence of ionic conductivities and dielectric relaxation rate constants. The energies of activation determined from self-diffusion coefficients in the series of alcohols are strikingly similar to those calculated for the same series of alcohols from both dielectric relaxation rate constants and ionic conductivities of dilute electrolytes. The experimental results are described in terms of an activated transport mechanism that is mediated by relaxation of the solution molecules. This microscopic picture of transport is postulated to be common to diffusion, dielectric relaxation, and ionic transport.

QSAR for cholinesterase inhibition by organophosphorus esters and CNDO/2 calculations for organophosphorus ester hydrolysis

NASA Technical Reports Server (NTRS)

Johnson, H.; Kenley, R. A.; Rynard, C.; Golub, M. A.

1985-01-01

Quantitative structure-activity relationships were derived for acetyl- and butyrylcholinesterase inhibition by various organophosphorus esters. Bimolecular inhibition rate constants correlate well with hydrophobic substituent constants, and with the presence or absence of catonic groups on the inhibitor, but not with steric substituent constants. CNDO/2 calculations were performed on a separate set of organophosphorus esters, RR'P(O)X, where R and R' are alkyl and/or alkoxy groups and X is fluorine, chlorine or a phenoxy group. For each subset with the same X, the CNDO-derived net atomic charge at the central phosphorus atom in the ester correlates well with the alkaline hydrolysis rate constant. For the whole set of esters with different X, two equations were derived that relate either charge and leaving group steric bulk, or orbital energy and bond order to the hydrogen hydrolysis rate constant.

QSAR for cholinesterase inhibition by organophosphorus esters and CNDO/2 calculations for organophosphorus ester hydrolysis. [quantitative structure-activity relationship, complete neglect of differential overlap

NASA Technical Reports Server (NTRS)

Johnson, H.; Kenley, R. A.; Rynard, C.; Golub, M. A.

1985-01-01

Quantitative structure-activity relationships were derived for acetyl- and butyrylcholinesterase inhibition by various organophosphorus esters. Bimolecular inhibition rate constants correlate well with hydrophobic substituent constants, and with the presence or absence of cationic groups on the inhibitor, but not with steric substituent constants. CNDO/2 calculations were performed on a separate set of organophosphorus esters, RR-primeP(O)X, where R and R-prime are alkyl and/or alkoxy groups and X is fluorine, chlorine or a phenoxy group. For each subset with the same X, the CNDO-derived net atomic charge at the central phosphorus atom in the ester correlates well with the alkaline hydrolysis rate constant. For the whole set of esters with different X, two equations were derived that relate either charge and leaving group steric bulk, or orbital energy and bond order to the hydrolysis rate constant.

Interaction of bovine serum albumin with N-acyl amino acid based anionic surfactants: Effect of head-group hydrophobicity.

PubMed

Ghosh, Subhajit; Dey, Joykrishna

2015-11-15

The function of a protein depends upon its structure and surfactant molecules are known to alter protein structure. For this reason protein-surfactant interaction is important in biological, pharmaceutical, and cosmetic industries. In the present work, interactions of a series of anionic surfactants having the same hydrocarbon chain length, but different amino acid head group, such as l-alanine, l-valine, l-leucine, and l-phenylalanine with the transport protein, bovine serum albumin (BSA), were studied at low surfactant concentrations using fluorescence and circular dichroism (CD) spectroscopy, and isothermal titration calorimetry (ITC). The results of fluorescence measurements suggest that the surfactant molecules bind simultaneously to the drug binding site I and II of the protein subdomain IIA and IIIA, respectively. The fluorescence as well as CD spectra suggest that the conformation of BSA goes to a more structured state upon surfactant binding at low concentrations. The binding constants of the surfactants were determined by the use of fluorescence as well as ITC measurements and were compared with that of the corresponding glycine-derived surfactant. The binding constant values clearly indicate a significant head-group effect on the BSA-surfactant interaction and the interaction is mainly hydrophobic in nature. Copyright © 2015 Elsevier Inc. All rights reserved.

Acidity of edge surface sites of montmorillonite and kaolinite

NASA Astrophysics Data System (ADS)

Liu, Xiandong; Lu, Xiancai; Sprik, Michiel; Cheng, Jun; Meijer, Evert Jan; Wang, Rucheng

2013-09-01

Acid-base chemistry of clay minerals is central to their interfacial properties, but up to now a quantitative understanding on the surface acidity is still lacking. In this study, with first principles molecular dynamics (FPMD) based vertical energy gap technique, we calculate the acidity constants of surface groups on (0 1 0)-type edges of montmorillonite and kaolinite, which are representatives of 2:1 and 1:1-type clay minerals, respectively. It shows that tbnd Si-OH and tbnd Al-OH2OH groups of kaolinite have pKas of 6.9 and 5.7 and those of montmorillonite have pKas of 7.0 and 8.3, respectively. For each mineral, the calculated pKas are consistent with the experimental ranges derived from fittings of titration curves, indicating that tbnd Si-OH and tbnd Al-OH2OH groups are the major acidic sites responsible to pH-dependent experimental observations. The effect of Mg substitution in montmorillonite is investigated and it is found that Mg substitution increases the pKas of the neighboring tbnd Si-OH and tbnd Si-OH2 groups by 2-3 pKa units. Furthermore, our calculation shows that the pKa of edge tbnd Mg-(OH2)2 is as high as 13.2, indicating the protonated state dominates under common pH. Together with previous adsorption experiments, our derived acidity constants suggest that tbnd Si-O- and tbnd Al-(OH)2 groups are the most probable edge sites for complexing heavy metal cations.

Room-temperature and temperature-dependent QSRR modelling for predicting the nitrate radical reaction rate constants of organic chemicals using ensemble learning methods.

PubMed

Gupta, S; Basant, N; Mohan, D; Singh, K P

2016-07-01

Experimental determinations of the rate constants of the reaction of NO3 with a large number of organic chemicals are tedious, and time and resource intensive; and the development of computational methods has widely been advocated. In this study, we have developed room-temperature (298 K) and temperature-dependent quantitative structure-reactivity relationship (QSRR) models based on the ensemble learning approaches (decision tree forest (DTF) and decision treeboost (DTB)) for predicting the rate constant of the reaction of NO3 radicals with diverse organic chemicals, under OECD guidelines. Predictive powers of the developed models were established in terms of statistical coefficients. In the test phase, the QSRR models yielded a correlation (r(2)) of >0.94 between experimental and predicted rate constants. The applicability domains of the constructed models were determined. An attempt has been made to provide the mechanistic interpretation of the selected features for QSRR development. The proposed QSRR models outperformed the previous reports, and the temperature-dependent models offered a much wider applicability domain. This is the first report presenting a temperature-dependent QSRR model for predicting the nitrate radical reaction rate constant at different temperatures. The proposed models can be useful tools in predicting the reactivities of chemicals towards NO3 radicals in the atmosphere, hence, their persistence and exposure risk assessment.

On the room temperature multiferroic BiFeO3: magnetic, dielectric and thermal properties

NASA Astrophysics Data System (ADS)

Lu, J.; Günther, A.; Schrettle, F.; Mayr, F.; Krohns, S.; Lunkenheimer, P.; Pimenov, A.; Travkin, V. D.; Mukhin, A. A.; Loidl, A.

2010-06-01

Magnetic dc susceptibility between 1.5 and 800 K, ac susceptibility and magnetization, thermodynamic properties, temperature dependence of radio and audio-wave dielectric constants and conductivity, contact-free dielectric constants at mm-wavelengths, as well as ferroelectric polarization are reported for single crystalline BiFeO3. A well developed anomaly in the magnetic susceptibility signals the onset of antiferromagnetic order close to 635 K. Beside this anomaly no further indications of phase or glass transitions are indicated in the magnetic dc and ac susceptibilities down to the lowest temperatures. The heat capacity has been measured from 2 K up to room temperature and significant contributions from magnon excitations have been detected. From the low-temperature heat capacity an anisotropy gap of the magnon modes of the order of 6 meV has been determined. The dielectric constants measured in standard two-point configuration are dominated by Maxwell-Wagner like effects for temperatures T > 300 K and frequencies below 1 MHz. At lower temperatures the temperature dependence of the dielectric constant and loss reveals no anomalies outside the experimental errors, indicating neither phase transitions nor strong spin phonon coupling. The temperature dependence of the dielectric constant was measured contact free at microwave frequencies. At room temperature the dielectric constant has an intrinsic value of 53. The loss is substantial and strongly frequency dependent indicating the predominance of hopping conductivity. Finally, in small thin samples we were able to measure the ferroelectric polarization between 10 and 200 K. The saturation polarization is of the order of 40 μC/cm2, comparable to reports in literature.

Cleavage of an amide bond by a ribozyme

NASA Technical Reports Server (NTRS)

Dai, X.; De Mesmaeker, A.; Joyce, G. F.; Miller, S. L. (Principal Investigator)

1995-01-01

A variant form of a group I ribozyme, optimized by in vitro evolution for its ability to catalyze magnesium-dependent phosphoester transfer reactions involving DNA substrates, also catalyzes the cleavage of an unactivated alkyl amide when that linkage is presented in the context of an oligodeoxynucleotide analog. Substrates containing an amide bond that joins either two DNA oligos, or a DNA oligo and a short peptide, are cleaved in a magnesium-dependent fashion to generate the expected products. The first-order rate constant, kcat, is 0.1 x 10(-5) min-1 to 1 x 10(-5) min-1 for the DNA-flanked substrates, which corresponds to a rate acceleration of more than 10(3) as compared with the uncatalyzed reaction.

Impedance spectroscopy studies on lead free Ba1-xMgx(Ti0.9Zr0.1)O3 ceramics

NASA Astrophysics Data System (ADS)

Ben Moumen, S.; Neqali, A.; Asbani, B.; Mezzane, D.; Amjoud, M.; Choukri, E.; Gagou, Y.; El Marssi, M.; Luk'yanchuk, Igor A.

2018-06-01

Ba1-xMgx(Ti0.9Zr0.1)O3 (x = 0.01 and 0.02) ceramics were prepared using the conventional solid state reaction. Rietveld refinement performed on X-ray diffraction patterns indicates that the samples are tetragonal crystal structure with P4mm space group. By increasing Mg content from 1 to 2% the unit cell volume decreased. Likewise, the grains size is greatly reduced from 10 μm to 4 μm. The temperature dependence of dielectric constants at different frequencies exhibited typical relaxor ferroelectric characteristic, with sensitive dependence in frequency and temperature for ac conductivity. The obtained activation energy values were correlated to the proposed conduction mechanisms.

Quantifying Protein-Ligand Binding Constants using Electrospray Ionization Mass Spectrometry: A Systematic Binding Affinity Study of a Series of Hydrophobically Modified Trypsin Inhibitors

NASA Astrophysics Data System (ADS)

Cubrilovic, Dragana; Biela, Adam; Sielaff, Frank; Steinmetzer, Torsten; Klebe, Gerhard; Zenobi, Renato

2012-10-01

NanoESI-MS is used for determining binding strengths of trypsin in complex with two different series of five congeneric inhibitors, whose binding affinity in solution depends on the size of the P3 substituent. The ligands of the first series contain a 4-amidinobenzylamide as P1 residue, and form a tight complex with trypsin. The inhibitors of the second series have a 2-aminomethyl-5-chloro-benzylamide as P1 group, and represent a model system for weak binders. The five different inhibitors of each group are based on the same scaffold and differ only in the length of the hydrophobic side chain of their P3 residue, which modulates the interactions in the S3/4 binding pocket of trypsin. The dissociation constants (KD) for high affinity ligands investigated by nanoESI-MS ranges from 15 nM to 450 nM and decreases with larger hydrophobic P3 side chains. Collision-induced dissociation (CID) experiments of five trypsin and benzamidine-based complexes show a correlation between trends in KD and gas-phase stability. For the second inhibitor series we could show that the effect of imidazole, a small stabilizing additive, can avoid the dissociation of the complex ions and as a result increases the relative abundance of weakly bound complexes. Here the KD values ranging from 2.9 to 17.6 μM, some 1-2 orders of magnitude lower than the first series. For both ligand series, the dissociation constants (KD) measured via nanoESI-MS were compared with kinetic inhibition constants (Ki) in solution.

The juggling act: Do student nurses who care for dependants need an adapted course? An applied policy research study.

PubMed

Kiernan, Matthew D; Proud, Carole; Jackson, Sue

2015-11-01

In line with many countries worldwide, the Department of Health mandate to Health Education England seeks to promote the diversity of applicants by widening participation in nurse education. A number of studies have explored the experience of non-traditional students undertaking nursing courses. This study aimed to explore and understand the experiences of student nurses undertaking their nurse education whilst caring for dependant family. The study used an applied qualitative research approached based on methods developed for applied social policy research. The study was undertaken in an institution of higher education in the North East of England. The study population consisted of a convenience sample of 14 respondents, 13 female and 1 male. Ten respondents lived with partners and 3 had disabled dependants within the family. The age range of dependent children ranged from 3months to 19years. Data was collected through focus groups and telephone interviews using a semi-structured interview schedule. Framework analysis was used to analyse the data. Three superordinate themes were identified, Altruism and Commitment, Maturity and Family and Social Mobility, that best encapsulate the characteristics that enable this group to function well and complete their nurse education. Analysis identified a highly motivated group of students who's individual accounts showed that their lives, whilst in nurse education, were a constant series of compromises and 'juggling' between the demands of the course and the demands of their families. This group of students do not need an adapted course, but instead wish for a realistic nursing course where expectations are managed in an honest way. Basic common sense and good management of nursing courses will help ensure that this motivated group of people achieve their goals with minimum hardship or difficulties. Copyright © 2015 Elsevier Ltd. All rights reserved.

An investigation of the kinetics of hydrogen chemisorption on iron metal surfaces

NASA Technical Reports Server (NTRS)

Shanabarger, M. R.

1982-01-01

The isothermal kinetics of H2, H2S, and O2 chemisorption onto epitaxially grown (III) oriented Fe films were studied. The measurements were made using the techniques of chemisorption induced resistance change and Auger electron spectroscopy (for adsorbed sulfur and oxygen). Also the origin of the chemisorption induced resistance change for these systems and its applicability to kinetic measurements were established. The chemisorption kinetics were interpreted as dissociative chemisorption via an adsorbed molecular species. The applicable rate constants were established. In none of the studies were the rate constants observed to be coverage dependent. By comparing the temperature dependence of the rate constants with absolute rate theory, the binding energies and activation energies of all the kinetic processes were obtained for the H2/Fe system. The initial sticking coefficient was pressure dependent for both the H2/Fe and H2S/Fe systems. This results from the step between the adsorbed molecular state and the dissociated chemisorbed state being the rate limiting step for absorption at certain pressures and temperatures. Estimates were obtained for the temperature dependence of the rate constants for the O2/Fe system.

Equivalent refractive-index structure constant of non-Kolmogorov turbulence.

PubMed

Li, Yujie; Zhu, Wenyue; Wu, Xiaoqing; Rao, Ruizhong

2015-09-07

The relationship between the non-Kolmogorov refractive-index structure constant and the Kolmogorov refractive-index structure constant is derived by using the refractive-index structure function and the variance of refractive-index fluctuations. It shows that the non-Kolmogorov structure constant is proportional to the Kolmogorov structure constant and the scaling factor depends on the outer scale and the spectral power law. For a fixed Kolmogorov structure constant, the non-Kolmogorov structure constant increases with a increasing outer scale for the power law less than 11/3, the trend is opposite for the power law greater than 11/3. This equivalent relation provides a way of obtaining the non-Kolmogorov structure constant by using the Kolmogorov structure constant.

Dielectric relaxation and magnetic properties of Ti and Zn co-doped GaFeO3

NASA Astrophysics Data System (ADS)

Raies, Imen; Dulmani, Shara A.; Amami, Mongi

2018-06-01

polycrystalline GaFeO3 and Ga0.98Zn0.02Fe0.98Ti0.02O3 were prepared by solid state reaction. They showed an orthorhombic crystal structure with Pc21n space group. The magnetic transition temperature decrease due to the dilution of the magnetic interaction. A noteworthy effect of substitution of multiple elements at the Ga and Fe-sites on dielectric constant and tangent loss of GaFeO3 has been observed. Complete studies of temperature (180-400 K) and frequency (10-107 Hz) dependence of dielectric constant and impedance have provided the effect of grains and grain boundaries on the conduction mechanism and dielectric relaxation of the material. Impedance spectroscopy results in the temperature range 160-400 K have revealed a distinct conduction process at grain and grain boundaries.

Structural, dielectric and magnetic studies of magnetoelectric trirutile Fe{sub 2}TeO{sub 6}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kaushik, S. D., E-mail: sdkaushik@csr.res.in; Sahu, B.; Mohapatra, S. R.

2016-05-23

We have investigated structural, magnetic and dielectric properties of Fe{sub 2}TeO{sub 6} which is a magnetoelectric antiferromagnet with the trirutile lattice. Rietveld analysis of room temperature X-ray diffraction data shows the phase purity of the sample with tetragonal trirutile structure (space group P4{sub 2}/mnm). The DC susceptibility measurement performed on polycrystalline powders exhibits antiferromagnetic ordering below transition temperature ~ 210K. The employment of Curie-Weiss law to inverse magnetic susceptibility only in the temperature range 350-260 K indicates the magnetic ordering starts developing before the transition temperature. The temperature dependent dielectric measurements show an intrinsic behavior of dielectric constant below 150more » K while a continuous increase in dielectric constant with temperature above 150 K may be attributed to a small increase in electrical conduction, known commonly in the literatures.« less

Coarse-graining, Electrostatics and pH effects in phospholipid systems

NASA Astrophysics Data System (ADS)

Travesset, Alex; Vangaveti, Sweta

2010-03-01

We introduce a minimal free energy describing the interaction of charged groups and counterions including both classical electrostatic and specific interactions. The predictions of the model are compared against the standard model for describing ions next to charged interfaces, consisting of Poisson-Boltzmann theory with additional constants describing ion binding, which are specific to the counterion and the interfacial charge (``chemical binding''). It is shown that the ``chemical'' model can be appropriately described by an underlying ``physical'' model over several decades in concentration, but the extracted binding constants are not uniquely defined, as they differ depending on the particular observable quantity being studied. It is also shown that electrostatic correlations for divalent (or higher valence) ions enhance the surface charge by increasing deprotonation, an effect not properly accounted within chemical models. The model is applied to the charged phospholipids phosphatidylserine, Phosphatidc acid and Phosphoinositides and implications for different biological processes are discussed.

Magnetic and dielectric characterization of Co{sub 0.9}Ni{sub 0.1}Fe{sub 2}O{sub 4} prepared by hydroxide co-precipitation method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mane, S. M., E-mail: manesagar99@gmail.com; Vijaysingh Mohite Patil Mahavidyalaya Natepute, Solapur-413109; Tirmali, P. M., E-mail: pravintirmali@gmail.com

2016-04-13

Co{sub 1–x} Ni{sub x}Fe{sub 2}O{sub 4} (where x=0.1) were prepared by using the hydroxide co-precipitation method. An obtained precipitate was sintered at 1100°C by microwave sintering technique. The structural analysis confirms the single-phase cubic spinel structure with Fd-3m space group. The magnetic characterization was carried out at temperature 300K.Saturation magnetisation and coercivity is 77.22 and 908 Oe. Irreversibility is observed between the ZFC and FC curves at 100 Oe. The variation in the dielectric constant and loss tangent are studied at room temperature with increasing frequency. Continues decrease in the the dielectric constant with increasing frequency shows inverse dependence onmore » frequency. Morphological and elemental studies were done by using the scanning electron microscope with EDAX.« less

Catalytic hydrodeoxygenation of methyl-substituted phenols: correlations of kinetic parameters with molecular properties.

PubMed

Massoth, F E; Politzer, P; Concha, M C; Murray, J S; Jakowski, J; Simons, Jack

2006-07-27

The hydrodeoxygenation of methyl-substituted phenols was carried out in a flow microreactor at 300 degrees C and 2.85 MPa hydrogen pressure over a sulfided CoMo/Al(2)O(3) catalyst. The primary reaction products were methyl-substituted benzene, cyclohexene, cyclohexane, and H(2)O. Analysis of the results suggests that two independent reaction paths are operative, one leading to aromatics and the other to partially or completely hydrogenated cyclohexanes. The reaction data were analyzed using Langmuir-Hinshelwood kinetics to extract the values of the reactant-to-catalyst adsorption constant and of the rate constants characterizing the two reaction paths. The adsorption constant was found to be the same for both reactions, suggesting that a single catalytic site center is operative in both reactions. Ab initio electronic structure calculations were used to evaluate the electrostatic potentials and valence orbital ionization potentials for all of the substituted phenol reactants. Correlations were observed between (a) the adsorption constant and the two reaction rate constants measured for various methyl-substitutions and (b) certain moments of the electrostatic potentials and certain orbitals' ionization potentials of the isolated phenol molecules. On the basis of these correlations to intrinsic reactant-molecule properties, a reaction mechanism is proposed for each pathway, and it is suggested that the dependencies of adsorption and reaction rates upon methyl-group substitution are a result of the substituents' effects on the electrostatic potential and orbitals rather than geometric (steric) effects.

Differential substrate behaviour of phenol and aniline derivatives during oxidation by horseradish peroxidase: kinetic evidence for a two-step mechanism.

PubMed

Gilabert, María Angeles; Hiner, Alexander N P; García-Ruiz, Pedro Antonio; Tudela, José; García-Molina, Francisco; Acosta, Manuel; García-Cánovas, Francisco; Rodríguez-López, José Neptuno

2004-06-01

The catalytic constant (k(cat)) and the second-order association constant of compound II with reducing substrate (k(5)) of horseradish peroxidase C (HRPC) acting on phenols and anilines have been determined from studies of the steady-state reaction velocities (V(0) vs. [S(0)]). Since k(cat)=k(2)k(6)/k(2)+k(6), and k(2) (the first-order rate constant for heterolytic cleavage of the oxygen-oxygen bond of hydrogen peroxide during compound I formation) is known, it has been possible to calculate the first-order rate constant for the transformation of each phenol or aniline by HRPC compound II (k(6)). The values of k(6) are quantitatively correlated to the sigma values (Hammett equation) and can be rationalized by an aromatic substrate oxidation mechanism in which the substrate donates an electron to the oxyferryl group in HRPC compound II, accompanied by two proton additions to the ferryl oxygen atom, one from the substrate and the other the protein or solvent. k(6) is also quantitatively correlated to the experimentally determined (13)C-NMR chemical shifts (delta(1)) and the calculated ionization potentials, E (HOMO), of the substrates. Similar dependencies were observed for k(cat) and k(5). From the kinetic analysis, the absolute values of the Michaelis constants for hydrogen peroxide and the reducing substrates (K(M)(H(2)O(2)) and K(M)(S)), respectively, were obtained.

Determination of temperature dependence of full matrix material constants of PZT-8 piezoceramics using only one sample.

PubMed

Zhang, Yang; Tang, Liguo; Tian, Hua; Wang, Jiyang; Cao, Wenwu; Zhang, Zhongwu

2017-08-15

Resonant ultrasound spectroscopy (RUS) was used to determine the temperature dependence of full matrix material constants of PZT-8 piezoceramics from room temperature to 100 °C. Property variations from sample to samples can be eliminated by using only one sample, so that data self-consistency can be guaranteed. The RUS measurement system error was estimated to be lower than 2.35%. The obtained full matrix material constants at different temperatures all have excellent self-consistency, which can help accurately predict device performance at high temperatures using finite element simulations.

The effect of presentation rate on implicit sequence learning in aging.

PubMed

Foster, Chris M; Giovanello, Kelly S

2017-02-01

Implicit sequence learning is thought to be preserved in aging when the to-be learned associations are first-order; however, when associations are second-order, older adults (OAs) tend to experience deficits as compared to young adults (YAs). Two experiments were conducted using a first (Experiment 1) and second-order (Experiment 2) serial-reaction time task. Stimuli were presented at a constant rate of either 800 milliseconds (fast) or 1200 milliseconds (slow). Results indicate that both age groups learned first-order dependencies equally in both conditions. OAs and YAs also learned second-order dependencies, but the learning of lag-2 information was significantly impacted by the rate of presentation for both groups. OAs showed significant lag-2 learning in slow condition while YAs showed significant lag-2 learning in the fast condition. The sensitivity of implicit sequence learning to the rate of presentation supports the idea that OAs and YAs different processing speeds impact the ability to build complex associations across time and intervening events.

Acid-Base Properties of Azo Dyes in Solution Studied Using Spectrophotometry and Colorimetry

NASA Astrophysics Data System (ADS)

Snigur, D. V.; Chebotarev, A. N.; Bevziuk, K. V.

2018-03-01

Colorimetry and spectrophotometry with chemometric data processing were used to study the acid-base properties of azo dyes in aqueous solution. The capabilities of both methods were compared. Ionization constants of all the functional groups of the azo compounds studied could be determined relative to the change in the specific color difference depending on the acidity of the medium. The colorimetric functions of ion-molecular forms of azo compounds used as an analytical signal allow us to obtain complete information on the acid-base equilibrium in a wide acidity range.

Chain decomposition of aqueous triethanolamine. [Gamma Radiation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schwarz, H.A.

A radiation-induced chain decomposition of aqueous triethanolamine into acetaldehyde and diethanolamine is reported. Chain lengths over 1000 have been observed, depending on pH, concentration, and radiation intensity. The chain propagation steps include OH group migration in the 2-hydroxy-1-(diethanolamino)ethyl radical and NR/sub 2/ migration in 1-hydroxy-2(diethanolamine)ethyl radical, each producing a 2-hydroxy-2-(diethanolamine)ethyl radical. Free-radical spectra and rate constants are given. Studies of diethanolamine and diethylethanolamine solutions gave similar free-radical spectra but much shorter chains.

The vibrational dependence of dissociative recombination: Rate constants for N{sub 2}{sup +}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guberman, Steven L., E-mail: slg@sci.org

Dissociative recombination rate constants are reported with electron temperature dependent uncertainties for the lowest 5 vibrational levels of the N{sub 2}{sup +} ground state. The rate constants are determined from ab initio calculations of potential curves, electronic widths, quantum defects, and cross sections. At 100 K electron temperature, the rate constants overlap with the exception of the third vibrational level. At and above 300 K, the rate constants for excited vibrational levels are significantly smaller than that for the ground level. It is shown that any experimentally determined total rate constant at 300 K electron temperature that is smaller thanmore » 2.0 × 10{sup −7} cm{sup 3}/s is likely to be for ions that have a substantially excited vibrational population. Using the vibrational level specific rate constants, the total rate constant is in very good agreement with that for an excited vibrational distribution found in a storage ring experiment. It is also shown that a prior analysis of a laser induced fluorescence experiment is quantitatively flawed due to the need to account for reactions with unknown rate constants. Two prior calculations of the dissociative recombination rate constant are shown to be inconsistent with the cross sections upon which they are based. The rate constants calculated here contribute to the resolution of a 30 year old disagreement between modeled and observed N{sub 2}{sup +} ionospheric densities.« less

The constant region affects antigen binding of antibodies to DNA by altering secondary structure.

PubMed

Xia, Yumin; Janda, Alena; Eryilmaz, Ertan; Casadevall, Arturo; Putterman, Chaim

2013-11-01

We previously demonstrated an important role of the constant region in the pathogenicity of anti-DNA antibodies. To determine the mechanisms by which the constant region affects autoantibody binding, a panel of isotype-switch variants (IgG1, IgG2a, IgG2b) was generated from the murine PL9-11 IgG3 autoantibody. The affinity of the PL9-11 antibody panel for histone was measured by surface plasmon resonance (SPR). Tryptophan fluorescence was used to determine wavelength shifts of the antibody panel upon binding to DNA and histone. Finally, circular dichroism spectroscopy was used to measure changes in secondary structure. SPR analysis revealed significant differences in histone binding affinity between members of the PL9-11 panel. The wavelength shifts of tryptophan fluorescence emission were found to be dependent on the antibody isotype, while circular dichroism analysis determined that changes in antibody secondary structure content differed between isotypes upon antigen binding. Thus, the antigen binding affinity is dependent on the particular constant region expressed. Moreover, the effects of antibody binding to antigen were also constant region dependent. Alteration of secondary structures influenced by constant regions may explain differences in fine specificity of anti-DNA antibodies between antibodies with similar variable regions, as well as cross-reactivity of anti-DNA antibodies with non-DNA antigens. Copyright © 2013 Elsevier Ltd. All rights reserved.

Size- and temperature-dependent Hamaker constants for heterogeneous systems of interacting nanoparticles

NASA Astrophysics Data System (ADS)

Pinchuk, P.; Pinchuk, A. O.

2016-09-01

Hamaker-Lifshitz constants are used to calculate van der Waals interaction forces between small particles in solution. Typically, these constants are size-independent and material specific. According to the Lifshitz theory, the Hamaker-Lifshitz constants can be calculated by taking integrals that include the dielectric permittivity, as a function of frequency, of the interacting particles and the medium around particles. The dielectric permittivity of interacting metal nanoparticles can be calculated using the free-electron Drude model for metals. For bulk metals, the Drude model does is size independent. However, the conducting electrons in small metal nanoparticles exhibit surface scattering, which changes the complex dielectric permittivity function. Additionally, the Drude model can be modified to include temperature dependence. That is, an increase in temperature leads to thermal volume expansion and increased phonon population, which affect the scattering rate of the electrons and the plasma frequency. Both of these terms contribute significantly to the Drude model for the dielectric permittivity of the particles. In this work, we show theoretically that scattering of the free conducting electrons inside noble metal nanoparticles with the size of 1 - 50 nm leads to size-dependent dielectric permittivity and Hamaker-Lifshitz constants. In addition, we calculate numerically the Hamaker-Lifshitz constants for a variety of temperatures. The results of the study might be of interest for understanding colloidal stability of metal nanoparticles.

Pressure-driven flow of a Herschel-Bulkley fluid with pressure-dependent rheological parameters

NASA Astrophysics Data System (ADS)

Panaseti, Pandelitsa; Damianou, Yiolanda; Georgiou, Georgios C.; Housiadas, Kostas D.

2018-03-01

The lubrication flow of a Herschel-Bulkley fluid in a symmetric long channel of varying width, 2h(x), is modeled extending the approach proposed by Fusi et al. ["Pressure-driven lubrication flow of a Bingham fluid in a channel: A novel approach," J. Non-Newtonian Fluid Mech. 221, 66-75 (2015)] for a Bingham plastic. Moreover, both the consistency index and the yield stress are assumed to be pressure-dependent. Under the lubrication approximation, the pressure at zero order depends only on x and the semi-width of the unyielded core is found to be given by σ(x) = -(1 + 1/n)h(x) + C, where n is the power-law exponent and the constant C depends on the Bingham number and the consistency-index and yield-stress growth numbers. Hence, in a channel of constant width, the width of the unyielded core is also constant, despite the pressure dependence of the yield stress, and the pressure distribution is not affected by the yield-stress function. With the present model, the pressure is calculated numerically solving an integro-differential equation and then the position of the yield surface and the two velocity components are computed using analytical expressions. Some analytical solutions are also derived for channels of constant and linearly varying widths. The lubrication solutions for other geometries are calculated numerically. The implications of the pressure-dependence of the material parameters and the limitations of the method are discussed.

Reproduction of bobwhites fed different dietary concentrations of an organophosphate insecticide, methamidophos

USGS Publications Warehouse

Stromborg, K.L.

1986-01-01

Pairs of first-year breeding bobwhites were fed constant or variable concentrations of methamidophos for 15 days, or a control diet in a pair-fed design in which they were matched by body weights to pairs in the constant group. Treatments for the constant group were 5.0, 7.8, 12.3, 19.2, and 30.0 ppm for 5 pairs at each concentration. The number of pairs per concentration and peak concentrations for the variable pairs were identical to the constant dosages. Concentrations for the variable group were increased by a factor of four during two 3-day periods in order to reach the peak concentrations on days 7?9 after which they were decreased by 18% every 3 days to correspond to an environmental half-time of 10.5 days. Food consumption, egg production, hatchability of eggs under artificial incubation, and survival of hatched chicks for 2 weeks were recorded for each pair during 15-day treatment and 21-day posttreatment periods. Mortality was high in the highest constant dosage (2/10) and the associated pair-fed groups (3/10). Food consumption and egg production rates were negatively dose-related during the treatment period in the constant and variable groups. The laying rate of pair-fed hens was reduced to the same extent as in the constant group. Reproductive inhibition was not permanent and pairs resumed laying after a dose-related recovery interval. No dose-related effects on hatchability or chick survival were detected. Furthermore, there was no evidence of a pesticide effect on reproduction in addition to that exerted through pesticide-induced anorexia.

Metal-organic complexes in geochemical processes: Estimation of standard partial molal thermodynamic properties of aqueous complexes between metal cations and monovalent organic acid ligands at high pressures and temperatures

NASA Astrophysics Data System (ADS)

Shock, Everetr L.; Koretsky, Carla M.

1995-04-01

Regression of standard state equilibrium constants with the revised Helgeson-Kirkham-Flowers (HKF) equation of state allows evaluation of standard partial molal entropies ( overlineSo) of aqueous metal-organic complexes involving monovalent organic acid ligands. These values of overlineSo provide the basis for correlations that can be used, together with correlation algorithms among standard partial molal properties of aqueous complexes and equation-of-state parameters, to estimate thermodynamic properties including equilibrium constants for complexes between aqueous metals and several monovalent organic acid ligands at the elevated pressures and temperatures of many geochemical processes which involve aqueous solutions. Data, parameters, and estimates are given for 270 formate, propanoate, n-butanoate, n-pentanoate, glycolate, lactate, glycinate, and alanate complexes, and a consistent algorithm is provided for making other estimates. Standard partial molal entropies of association ( Δ -Sro) for metal-monovalent organic acid ligand complexes fall into at least two groups dependent upon the type of functional groups present in the ligand. It is shown that isothermal correlations among equilibrium constants for complex formation are consistent with one another and with similar correlations for inorganic metal-ligand complexes. Additional correlations allow estimates of standard partial molal Gibbs free energies of association at 25°C and 1 bar which can be used in cases where no experimentally derived values are available.

Low noise constant current source for bias dependent noise measurements

DOE Office of Scientific and Technical Information (OSTI.GOV)

Talukdar, D.; Bose, Suvendu; Bardhan, K. K.

2011-01-15

A low noise constant current source used for measuring the 1/f noise in disordered systems in ohmic as well as nonohmic regime is described. The source can supply low noise constant current starting from as low as 1 {mu}A to a few tens of milliampere with a high voltage compliance limit of around 20 V. The constant current source has several stages, which can work in a standalone manner or together to supply the desired value of load current. The noise contributed by the current source is very low in the entire current range. The fabrication of a low noisemore » voltage preamplifier modified for bias dependent noise measurements and based on the existing design available in the MAT04 data sheet is also described.« less

Size-dependent Hamaker constants for silver and gold nanoparticles

NASA Astrophysics Data System (ADS)

Pinchuk, Pavlo; Jiang, Ke

2015-08-01

Hamaker-Lifshitz constants are material specific constants that are used to calculate van der Waals interaction forces between small particles in solution. Typically, these constants are size-independent and material specific. According to the Lifshitz theory, the Hamaker-Lifshitz constants can be calculated by taking integrals that include the dielectric permittivity, as a function of frequency, of the interacting particles and the medium around particles. The dielectric permittivity of interacting metal nanoparticles can be calculated using the Drude model, which is based on the assumption of motion of free conducting electrons. For bulk metals, the Drude model does not predict any sizedependence of the dielectric permittivity. However, the conducting electrons in small noble metal nanoparticles (R ~ 10nm) exhibit surface scattering, which changes the complex permittivity function. In this work, we show theoretically that scattering of the free conducting electrons inside silver and gold nanoparticles with the size of 1 - 50 nm leads to size-dependent dielectric permittivity and Hamaker-Lifshitz constants. We calculate numerically the Hamaker-Lifshitz constants for silver and gold nanoparticles with different diameters. The results of the study might be of interests for understanding colloidal stability of metal nanoparticles.

Calculation of individual isotope equilibrium constants for implementation in geochemical models

USGS Publications Warehouse

Thorstenson, Donald C.; Parkhurst, David L.

2002-01-01

Theory is derived from the work of Urey to calculate equilibrium constants commonly used in geochemical equilibrium and reaction-transport models for reactions of individual isotopic species. Urey showed that equilibrium constants of isotope exchange reactions for molecules that contain two or more atoms of the same element in equivalent positions are related to isotope fractionation factors by , where is n the number of atoms exchanged. This relation is extended to include species containing multiple isotopes, for example and , and to include the effects of nonideality. The equilibrium constants of the isotope exchange reactions provide a basis for calculating the individual isotope equilibrium constants for the geochemical modeling reactions. The temperature dependence of the individual isotope equilibrium constants can be calculated from the temperature dependence of the fractionation factors. Equilibrium constants are calculated for all species that can be formed from and selected species containing , in the molecules and the ion pairs with where the subscripts g, aq, l, and s refer to gas, aqueous, liquid, and solid, respectively. These equilibrium constants are used in the geochemical model PHREEQC to produce an equilibrium and reaction-transport model that includes these isotopic species. Methods are presented for calculation of the individual isotope equilibrium constants for the asymmetric bicarbonate ion. An example calculates the equilibrium of multiple isotopes among multiple species and phases.

Distance-dependent diffusion-controlled reaction of •NO and O2•- at chemical equilibrium with ONOO-.

PubMed

Botti, Horacio; Möller, Matías N; Steinmann, Daniel; Nauser, Thomas; Koppenol, Willem H; Denicola, Ana; Radi, Rafael

2010-12-16

The fast reaction of (•)NO and O(2)(•-) to give ONOO(-) has been extensively studied at irreversible conditions, but the reasons for the wide variations in observed forward rate constants (3.8 ≤ k(f) ≤ 20 × 10(9) M(-1) s(-1)) remain unexplained. We characterized the diffusion-dependent aqueous (pH > 12) chemical equilibrium of the form (•)NO + O(2)(•-) = ONOO(-) with respect to its dependence on temperature, viscosity, and [ONOO(-)](eq) by determining [ONOO(-)](eq) and [(•)NO](eq). The equilibrium forward reaction rate constant (k(f)(eq)) has negative activation energy, in contrast to that found under irreversible conditions. In contradiction to the law of mass action, we demonstrate that the equilibrium constant depends on ONOO(-) concentration. Therefore, a wide range of k(f)(eq) values could be derived (7.5-21 × 10(9) M(-1) s(-1)). Of general interest, the variations in k(f) can thus be explained by its dependence on the distance between ONOO(-) particles (sites of generation of (•)NO and O(2)(•-)).

COMPUTATION OF ℛ IN AGE-STRUCTURED EPIDEMIOLOGICAL MODELS WITH MATERNAL AND TEMPORARY IMMUNITY.

PubMed

Feng, Zhilan; Han, Qing; Qiu, Zhipeng; Hill, Andrew N; Glasser, John W

2016-03-01

For infectious diseases such as pertussis, susceptibility is determined by immunity, which is chronological age-dependent. We consider an age-structured epidemiological model that accounts for both passively acquired maternal antibodies that decay and active immunity that wanes, permitting reinfection. The model is a 6-dimensional system of partial differential equations (PDE). By assuming constant rates within each age-group, the PDE system can be reduced to an ordinary differential equation (ODE) system with aging from one age-group to the next. We derive formulae for the effective reproduction number ℛ and provide their biological interpretation in some special cases. We show that the disease-free equilibrium is stable when ℛ < 1 and unstable if ℛ > 1.

How fundamental are fundamental constants?

NASA Astrophysics Data System (ADS)

Duff, M. J.

2015-01-01

I argue that the laws of physics should be independent of one's choice of units or measuring apparatus. This is the case if they are framed in terms of dimensionless numbers such as the fine structure constant, ?. For example, the standard model of particle physics has 19 such dimensionless parameters whose values all observers can agree on, irrespective of what clock, rulers or scales? they use to measure them. Dimensional constants, on the other hand, such as ?, c, G, e and k ?, are merely human constructs whose number and values differ from one choice of units to the next. In this sense, only dimensionless constants are 'fundamental'. Similarly, the possible time variation of dimensionless fundamental 'constants' of nature is operationally well defined and a legitimate subject of physical enquiry. By contrast, the time variation of dimensional constants such as ? or ? on which a good many (in my opinion, confusing) papers have been written, is a unit-dependent phenomenon on which different observers might disagree depending on their apparatus. All these confusions disappear if one asks only unit-independent questions. We provide a selection of opposing opinions in the literature and respond accordingly.

Improving Image Quality of Coronary Computed Tomography Angiography Using Patient Weight and Height-Dependent Scan Trigger Threshold.

PubMed

Kang, Deqiang; Hua, Haiqin; Peng, Nan; Zhao, Jing; Wang, Zhiqun

2017-04-01

We aim to improve the image quality of coronary computed tomography angiography (CCTA) by using personalized weight and height-dependent scan trigger threshold. This study was divided into two parts. First, we performed and analyzed the 100 scheduled CCTA data, which were acquired by using body mass index-dependent Smart Prep sequence (trigger threshold ranged from 80 Hu to 250 Hu based on body mass index). By identifying the cases of high quality image, a linear regression equation was established to determine the correlation among the Smart Prep threshold, height, and body weight. Furthermore, a quick search table was generated for weight and height-dependent Smart Prep threshold in CCTA scan. Second, to evaluate the effectiveness of the new individual threshold method, an additional 100 consecutive patients were divided into two groups: individualized group (n = 50) with weight and height-dependent threshold and control group (n = 50) with the conventional constant threshold of 150 HU. Image quality was compared between the two groups by measuring the enhancement in coronary artery, aorta, left and right ventricle, and inferior vena cava. By visual inspection, image quality scores were performed to compare between the two groups. Regression equation between Smart Prep threshold (K, Hu), height (H, cm), and body weight (BW, kg) was K = 0.811 × H + 1.917 × BW - 99.341. When compared to the control group, the individualized group presented an average overall increase of 12.30% in enhancement in left main coronary artery, 12.94% in proximal right coronary artery, and 10.6% in aorta. Correspondingly, the contrast-to-noise ratios increased by 26.03%, 27.08%, and 23.17%, respectively, and by 633.1% in contrast between aorta and left ventricle. Meanwhile, the individualized group showed an average overall decrease of 22.7% in enhancement of right ventricle and 32.7% in inferior vena cava. There was no significant difference of the image noise between the two groups (P > .05). By visual inspection, the image quality score of the individualized group was higher than that of the control group. Using personalized weight and height-dependent Smart Prep threshold to adjust scan trigger time can significantly improve the image quality of CCTA. Copyright © 2017 The Association of University Radiologists. Published by Elsevier Inc. All rights reserved.

A Virtual Mixture Approach to the Study of Multistate Equilibrium: Application to Constant pH Simulation in Explicit Water

PubMed Central

Wu, Xiongwu; Brooks, Bernard R.

2015-01-01

Chemical and thermodynamic equilibrium of multiple states is a fundamental phenomenon in biology systems and has been the focus of many experimental and computational studies. This work presents a simulation method to directly study the equilibrium of multiple states. This method constructs a virtual mixture of multiple states (VMMS) to sample the conformational space of all chemical states simultaneously. The VMMS system consists of multiple subsystems, one for each state. The subsystem contains a solute and a solvent environment. The solute molecules in all subsystems share the same conformation but have their own solvent environments. Transition between states is implicated by the change of their molar fractions. Simulation of a VMMS system allows efficient calculation of relative free energies of all states, which in turn determine their equilibrium molar fractions. For systems with a large number of state transition sites, an implicit site approximation is introduced to minimize the cost of simulation. A direct application of the VMMS method is for constant pH simulation to study protonation equilibrium. Applying the VMMS method to a heptapeptide of 3 ionizable residues, we calculated the pKas of those residues both with all explicit states and with implicit sites and obtained consistent results. For mouse epidermal growth factor of 9 ionizable groups, our VMMS simulations with implicit sites produced pKas of all 9 ionizable groups and the results agree qualitatively with NMR measurement. This example demonstrates the VMMS method can be applied to systems of a large number of ionizable groups and the computational cost scales linearly with the number of ionizable groups. For one of the most challenging systems in constant pH calculation, SNase Δ+PHS/V66K, our VMMS simulation shows that it is the state-dependent water penetration that causes the large deviation in lysine66’s pKa. PMID:26506245

A Virtual Mixture Approach to the Study of Multistate Equilibrium: Application to Constant pH Simulation in Explicit Water.

PubMed

Wu, Xiongwu; Brooks, Bernard R

2015-10-01

Chemical and thermodynamic equilibrium of multiple states is a fundamental phenomenon in biology systems and has been the focus of many experimental and computational studies. This work presents a simulation method to directly study the equilibrium of multiple states. This method constructs a virtual mixture of multiple states (VMMS) to sample the conformational space of all chemical states simultaneously. The VMMS system consists of multiple subsystems, one for each state. The subsystem contains a solute and a solvent environment. The solute molecules in all subsystems share the same conformation but have their own solvent environments. Transition between states is implicated by the change of their molar fractions. Simulation of a VMMS system allows efficient calculation of relative free energies of all states, which in turn determine their equilibrium molar fractions. For systems with a large number of state transition sites, an implicit site approximation is introduced to minimize the cost of simulation. A direct application of the VMMS method is for constant pH simulation to study protonation equilibrium. Applying the VMMS method to a heptapeptide of 3 ionizable residues, we calculated the pKas of those residues both with all explicit states and with implicit sites and obtained consistent results. For mouse epidermal growth factor of 9 ionizable groups, our VMMS simulations with implicit sites produced pKas of all 9 ionizable groups and the results agree qualitatively with NMR measurement. This example demonstrates the VMMS method can be applied to systems of a large number of ionizable groups and the computational cost scales linearly with the number of ionizable groups. For one of the most challenging systems in constant pH calculation, SNase Δ+PHS/V66K, our VMMS simulation shows that it is the state-dependent water penetration that causes the large deviation in lysine66's pKa.

Calculation of the acid-base equilibrium constants at the alumina/electrolyte interface from the ph dependence of the adsorption of singly charged ions (Na+, Cl-)

NASA Astrophysics Data System (ADS)

Gololobova, E. G.; Gorichev, I. G.; Lainer, Yu. A.; Skvortsova, I. V.

2011-05-01

A procedure was proposed for the calculation of the acid-base equilibrium constants at an alumina/electrolyte interface from experimental data on the adsorption of singly charged ions (Na+, Cl-) at various pH values. The calculated constants (p K {1/0}= 4.1, p K {2/0}= 11.9, p K {3/0}= 8.3, and p K {4/0}= 7.7) are shown to agree with the values obtained from an experimental pH dependence of the electrokinetic potential and the results of potentiometric titration of Al2O3 suspensions.

Laser-driven interactions and resultant instabilities in materials with high dielectric constant

NASA Astrophysics Data System (ADS)

Rajpoot, Moolchandra; Dixit, Sanjay

2015-07-01

An analytical investigation of nonlinear interactions resulting in parametric amplification of acoustic wave is made by obtaining the dispersion relation using hydrodynamic model of inhomogeneous plasma by applying large static field at an arbitrary angle with the pump wave. The investigation shows that many early studies have neglected dependence of dielectric constant on deformation of materials but deformation of materials does infect depends on the dielectric constant of medium. Thus we have assumed to high dielectric material like BaTiO3 which resulted in substantially high growth rate of threshold electric field which opens a new dimension to study nonlinear interactions and instabilities.

Influence of Analyte Concentration on Stability Constant Values Determined by Capillary Electrophoresis.

PubMed

Sursyakova, Viktoria V; Burmakina, Galina V; Rubaylo, Anatoly I

2016-08-01

The influence of analyte concentration when compared with the concentration of a charged ligand in background electrolyte (BGE) on the measured values of electrophoretic mobilities and stability constants (association, binding or formation constants) is studied using capillary electrophoresis (CE) and a dynamic mathematical simulator of CE. The study is performed using labile complexes (with fast kinetics) of iron (III) and 5-sulfosalicylate ions (ISC) as an example. It is shown that because the ligand concentration in the analyte zone is not equal to that in BGE, considerable changes in the migration times and electrophoretic mobilities are observed, resulting in systematic errors in the stability constant values. Of crucial significance is the slope of the dependence of the electrophoretic mobility decrease on the ligand equilibrium concentration. Without prior information on this dependence to accurately evaluate the stability constants for similar systems, the total ligand concentration must be at least >50-100 times higher than the total concentration of analyte. Experimental ISC peak fronting and the difference between the direction of the experimental pH dependence of the electrophoretic mobility decrease and the mathematical simulation allow assuming the presence of capillary wall interaction. © The Author 2016. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Cationic drug pharmacokinetics in diseased livers determined by fibrosis index, hepatic protein content, microsomal activity, and nature of drug.

PubMed

Hung, Daniel Y; Chang, Ping; Cheung, Kee; McWhinney, Brett; Masci, Paul P; Weiss, Michael; Roberts, Michael S

2002-06-01

The disposition kinetics of six cationic drugs in perfused diseased and normal rat livers were determined by multiple indicator dilution and related to the drug physicochemical properties and liver histopathology. A carbon tetrachloride (CCl(4))-induced acute hepatocellular injury model had a higher fibrosis index (FI), determined by computer-assisted image analysis, than did an alcohol-induced chronic hepatocellular injury model. The alcohol-treated group had the highest hepatic alpha(1)-acid glycoprotein, microsomal protein (MP), and cytochrome P450 (P450) concentrations. Various pharmacokinetic parameters could be related to the octanol-water partition coefficient (log P(app)) of the drug as a surrogate for plasma membrane partition coefficient and affinity for MP or P450, the dependence being lower in the CCl(4)-treated group and higher in the alcohol-treated group relative to controls. Stepwise regression analysis showed that hepatic extraction ratio, permeability-surface area product, tissue-binding constant, intrinsic clearance, partition ratio of influx (k(in)) and efflux rate constant (k(out)), and k(in)/k(out) were related to physicochemical properties of drug (log P(app) or pK(a)) and liver histopathology (FI, MP, or P450). In addition, hepatocyte organelle ion trapping of cationic drugs was evident in all groups. It is concluded that fibrosis-inducing hepatic disease effects on cationic drug disposition in the liver may be predicted from drug properties and liver histopathology.

A novel model to predict gas-phase hydroxyl radical oxidation kinetics of polychlorinated compounds.

PubMed

Luo, Shuang; Wei, Zongsu; Spinney, Richard; Yang, Zhihui; Chai, Liyuan; Xiao, Ruiyang

2017-04-01

In this study, a novel model based on aromatic meta-substituent grouping was presented to predict the second-order rate constants (k) for OH oxidation of PCBs in gas-phase. Since the oxidation kinetics are dependent on the chlorination degree and position, we hypothesized that it may be more accurate for k value prediction if we group PCB congeners based on substitution positions (i.e., ortho (o), meta (m), and para (p)). To test this hypothesis, we examined the correlation of polarizability (α), a quantum chemical based descriptor for k values, with an empirical Hammett constant (σ + ) on each substitution position. Our result shows that α is highly linearly correlated to ∑σ o,m,p + based on aromatic meta-substituents leading to the grouping based predictive model. With the new model, the calculated k values exhibited an excellent agreement with experimental measurements, and greater predictive power than the quantum chemical based quantitative structure activity relationship (QSAR) model. Further, the relationship of α and ∑σ o,m,p + for PCDDs congeners, together with highest occupied molecular orbital (HOMO) distribution, were used to validate the aromatic meta-substituent grouping method. This newly developed model features a combination of good predictability of quantum chemical based QSAR model and simplicity of Hammett relationship, showing a great potential for fast and computational tractable prediction of k values for gas-phase OH oxidation of polychlorinated compounds. Copyright © 2017 Elsevier Ltd. All rights reserved.

Wavelength dependence of Verdet constant of Tb{sup 3+}:Y{sub 2}O{sub 3} ceramics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Snetkov, I. L., E-mail: snetkov@appl.sci-nnov.ru; Palashov, O. V.; Permin, D. A.

2016-04-18

Samples of the magneto-active material—Tb{sup 3+}:Y{sub 2}O{sub 3} ceramics with Tb{sup 3+} ion concentrations of 10%, 20%, 30%, and 100% (Tb{sub 2}O{sub 3})—were prepared and studied. The wavelength dependence of Verdet constant in the 380 nm–1750 nm range was approximated for all investigated ceramic samples and was predicted for a pure Tb{sub 2}O{sub 3} material. Tb{sub 2}O{sub 3} ceramics demonstrates a more than three times higher Verdet constant in comparison with terbium gallium garnet crystal or ceramics. The linear dependence of the Verdet constant on Tb{sup 3+} ion concentration in the Tb{sup 3+}:Y{sub 2}O{sub 3} ceramics was demonstrated. The obtained data willmore » be useful for fabricating magneto-optical elements of Faraday devices based on Tb{sup 3+}:Y{sub 2}O{sub 3} with arbitrary Tb{sup 3+} ion concentration operating at room temperature in the wavelength range of 380 nm–1750 nm.« less

Infrared and Raman studies of hydrogen bonded complexes involving acetone, acetophenone and benzophenone—I. Thermodynamic constants and frequency shifts of the ν OH and ν CO stretching vibrations

NASA Astrophysics Data System (ADS)

Thijs, R.; Zeegers-Huyskens, Th.

The hydrogen bonded complexes between phenol derivatives and acetone ( I), acetophenone ( II) and benzophenone ( III) have been studied in carbon tetrachloride solution by i.r. spectroscopy. The formation constants, the enthalpies of complex formation, the Δν OH and Δν CO values have been determined. For a given phenol derivative, the thermodynamic constants and Δν OH are ordered according to I > II > III and the influence of a substituent implanted on the phenolic ring can be expressed by the Hammett relationship. The ϱ coefficients of the Hammett equation are related to the complexation enthalpies. The Badger—Bauer relation is valid for the three bases. The comparison with complexes involving other carbonyl bases allows to precise the influence of the substituent implanted on the carbonyl group. The Δν OH values obey the dual substituent parameter equation using σ I and σ +R; the ϱ I/ϱ R ratio is higher than one. The Δν CO values are shown to depend on the complexation enthalpy and on the delocalization effect of the substituents.

Mussel-inspired histidine-based transient network metal coordination hydrogels

PubMed Central

Fullenkamp, Dominic E.; He, Lihong; Barrett, Devin G.; Burghardt, Wesley R.; Messersmith, Phillip B.

2013-01-01

Transient network hydrogels cross-linked through histidine-divalent cation coordination bonds were studied by conventional rheologic methods using histidine-modified star poly(ethylene glycol) (PEG) polymers. These materials were inspired by the mussel, which is thought to use histidine-metal coordination bonds to impart self-healing properties in the mussel byssal thread. Hydrogel viscoelastic mechanical properties were studied as a function of metal, pH, concentration, and ionic strength. The equilibrium metal-binding constants were determined by dilute solution potentiometric titration of monofunctional histidine-modified methoxy-PEG and were found to be consistent with binding constants of small molecule analogs previously studied. pH-dependent speciation curves were then calculated using the equilibrium constants determined by potentiometric titration, providing insight into the pH dependence of histidine-metal ion coordination and guiding the design of metal coordination hydrogels. Gel relaxation dynamics were found to be uncorrelated with the equilibrium constants measured, but were correlated to the expected coordination bond dissociation rate constants. PMID:23441102

Microscopic theoretical study of frequency dependent dielectric constant of heavy fermion systems

NASA Astrophysics Data System (ADS)

Shadangi, Keshab Chandra; Rout, G. C.

2017-05-01

The dielectric polarization and the dielectric constant plays a vital role in the deciding the properties of the Heavy Fermion Systems. In the present communication we consider the periodic Anderson's Model which consists of conduction electron kinetic energy, localized f-electron kinetic energy and the hybridization between the conduction and localized electrons, besides the Coulomb correlation energy. We calculate dielectric polarization which involves two particle Green's functions which are calculated by using Zubarev's Green's function technique. Using the equations of motion of the fermion electron operators. Finally, the temperature and frequency dependent dielectric constant is calculated from the dielectric polarization function. The charge susceptibility and dielectric constant are computed numerically for different physical parameters like the position (Ef) of the f-electron level with respect to fermi level, the strength of the hybridization (V) between the conduction and localized f-electrons, Coulomb correlation potential temperature and optical phonon wave vector (q). The results will be discussed in a reference to the experimental observations of the dielectric constants.

1,3-syn-Diaxial Repulsion of Typical Protecting Groups Used in Carbohydrate Chemistry in 3-O-Substituted Derivatives of Isopropyl d-Idopyranosides.

PubMed

Komarova, Bozhena S; Gerbst, Alexey G; Finogenova, Anastasiia M; Dmitrenok, Andrey S; Tsvetkov, Yury E; Nifantiev, Nikolay E

2017-09-01

The strength of 1,3-syn-diaxial repulsion was evaluated for main types of protecting groups (alkyl, silyl, and acyl) usually used in carbohydrate chemistry. As molecular probes for this study, derivatives of isopropyl 2-O-benzyl-4,6-O-benzylidene-α-d-idopyranoside bearing allyl, acetyl, and tert-butyldiphenylsilyl (TBDPS) protecting groups at O-3 were prepared from p-methoxyphenyl d-galactopyranoside. The equilibrium between O S 2 and 4 C 1 conformations in these compounds was investigated using 3 J H,H and 3 J C,H coupling constants that were determined from 1D 1 H NMR and 2D J-resolved HMBC spectra in various solvents. The analysis of the corresponding coupling constants calculated using DFT/B3LYP/pcJ-1 approximation applied to conformations optimized at DFT/B3LYP/6-311++G** level supported the investigation. Proportions of conformers in the equilibrium revealed the highest repulsion between the 3-allyloxy group and the isopropoxy aglycon and its dependence on the solvent polarity. Differences in the conformational behavior of 3-O-allyl and 3-O-acetyl-α-d-idopyranoside derivatives complied with the notion that higher electron density on O-3 increased 1,3-syn-diaxial repulsion. 3-O-TBDPS derivative existed mainly in 4 C 1 conformation. The attenuation of the 1,3-syn-diaxial repulsive interaction indicates that TBDPS has stereoelectronic properties that may have significance in context of fixing unnatural pyranoside conformation with the help of silyl groups but have been disregarded until now.

Pressure Dependences of Elastic Constants of AMg6 Aluminum-Magnesium Alloy and n-AMg6/C60 Nanocomposite Alloy

NASA Astrophysics Data System (ADS)

Prokhorov, V. M.; Gromnitskaya, E. L.

2018-04-01

The ultrasonic study results for dependence of the elastic wave velocities and second-order elasticity coefficients of the polycrystalline aluminum alloy AMg6 and its nanocomposite n-AMg6/C60 on hydrostatic pressure up to 1.6 GPa have been described. The ultrasonic research has been carried out using a highpressure ultrasonic piezometer based on the piston-cylinder device. The pressure derivatives of the secondorder elastic constants of these materials established in the present study have been compared with the results of the third-order elastic constants measurements of the test alloys using the Thurston-Brugger method. Involving available literature data, we determined the relationships between the pressure derivatives of the second-order elastic constants of the AMg6 alloy and the Mg-content and nanostructuring.

An engineering method for estimating notch-size effect in fatigue tests on steel

NASA Technical Reports Server (NTRS)

Kuhn, Paul; Hardrath, Herbert F

1952-01-01

Neuber's proposed method of calculating a practical factor of stress concentration for parts containing notches of arbitrary size depends on the knowledge of a "new material constant" which can be established only indirectly. In this paper, the new constant has been evaluated for a large variety of steels from fatigue tests reported in the literature, attention being confined to stresses near the endurance limit. Reasonably satisfactory results were obtained with the assumption that the constant depends only on the tensile strength of the steel. Even in cases where the notches were cracks of which only the depth was known, reasonably satisfactory agreement was found between calculated and experimental factors. It is also shown that the material constant can be used in an empirical formula to estimate the size effect on unnotched specimens tested in bending fatigue.

HO + CO reaction rates and H/D kinetic isotope effects: master equation models with ab initio SCTST rate constants.

PubMed

Weston, Ralph E; Nguyen, Thanh Lam; Stanton, John F; Barker, John R

2013-02-07

Ab initio microcanonical rate constants were computed using Semi-Classical Transition State Theory (SCTST) and used in two master equation formulations (1D, depending on active energy with centrifugal corrections, and 2D, depending on total energy and angular momentum) to compute temperature-dependent rate constants for the title reactions using a potential energy surface obtained by sophisticated ab initio calculations. The 2D master equation was used at the P = 0 and P = ∞ limits, while the 1D master equation with centrifugal corrections and an empirical energy transfer parameter could be used over the entire pressure range. Rate constants were computed for 75 K ≤ T ≤ 2500 K and 0 ≤ [He] ≤ 10(23) cm(-3). For all temperatures and pressures important for combustion and for the terrestrial atmosphere, the agreement with the experimental rate constants is very good, but at very high pressures and T ≤ 200 K, the theoretical rate constants are significantly smaller than the experimental values. This effect is possibly due to the presence in the experiments of dimers and prereactive complexes, which were not included in the model calculations. The computed H/D kinetic isotope effects are in acceptable agreement with experimental data, which show considerable scatter. Overall, the agreement between experimental and theoretical H/D kinetic isotope effects is much better than in previous work, and an assumption of non-RRKM behavior does not appear to be needed to reproduce experimental observations.

Asymptotic symmetries on Killing horizons

NASA Astrophysics Data System (ADS)

Koga, Jun-Ichirou

2001-12-01

We investigate asymptotic symmetries regularly defined on spherically symmetric Killing horizons in Einstein theory with or without the cosmological constant. These asymptotic symmetries are described by asymptotic Killing vectors, along which the Lie derivatives of perturbed metrics vanish on a Killing horizon. We derive the general form of the asymptotic Killing vectors and find that the group of asymptotic symmetries consists of rigid O(3) rotations of a horizon two-sphere and supertranslations along the null direction on the horizon, which depend arbitrarily on the null coordinate as well as the angular coordinates. By introducing the notion of asymptotic Killing horizons, we also show that local properties of Killing horizons are preserved not only under diffeomorphisms but also under nontrivial transformations generated by the asymptotic symmetry group. Although the asymptotic symmetry group contains the Diff(S1) subgroup, which results from supertranslations dependent only on the null coordinate, it is shown that the Poisson brackets algebra of the conserved charges conjugate to asymptotic Killing vectors does not acquire nontrivial central charges. Finally, by considering extended symmetries, we discuss the fact that unnatural reduction of the symmetry group is necessary in order to obtain the Virasoro algebra with nontrivial central charges, which is not justified when we respect the spherical symmetry of Killing horizons.

The temperature dependence of the rate constant for the reaction of hydroxyl radicals with nitric acid

NASA Technical Reports Server (NTRS)

Kurylo, M. J.; Cornett, K. D.; Murphy, J. L.

1982-01-01

The rate constant for the reaction of hydroxyl radicals with nitric acid in the 225-443 K temperature range has been measured by means of the flash photolysis resonance fluorescence technique. Above 300 K, the rate constant levels off in a way that can only be explained by the occurrence of two reaction channels, of which one, operative at low temperatures, proceeds through the formation of an adduct intermediate. The implications of these rate constant values for stratospheric reaction constants is discussed.

L-tryptophan-induced electron transport across supported lipid bilayers: an alkyl-chain tilt-angle, and bilayer-symmetry dependence.

PubMed

Sarangi, Nirod Kumar; Patnaik, Archita

2012-12-21

Molecular orientation-dependent electron transport across supported 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) lipid bilayers (SLBs) on semiconducting indium tin oxide (ITO) is reported with an aim towards potential nanobiotechnological applications. A bifunctional strategy is adopted to form symmetric and asymmetric bilayers of DPPC that interact with L-tryptophan, and are analyzed by surface manometry and atomic force microscopy. Polarization-dependent real-time Fourier transform infrared reflection absorption spectroscopy (FT-IRRAS) analysis of these SLBs reveals electrostatic, hydrogen-bonding, and cation-π interactions between the polar head groups of the lipid and the indole side chains. Consequently, a molecular tilt arises from the effective interface dipole, facilitating electron transport across the ITO-anchored SLBs in the presence of an internal Fe(CN)(6)(4-/3-) redox probe. The incorporation of tryptophan enhances the voltammetric features of the SLBs. The estimated electron-transfer rate constants for symmetric and asymmetric bilayers (k(s) = 2.0×10(-2) and 2.8×10(-2) s(-1)) across the two-dimensional (2D) ordered DPPC/tryptophan SLBs are higher compared to pure DPPC SLBs (k(s) = 3.2×10(-3) and 3.9×10(-3) s(-1)). In addition, they are molecular tilt-dependent, as it is the case with the standard apparent rate constants k(app)(0), estimated from electrochemical impedance spectroscopy and bipotentiostatic experiments with a Pt ultramicroelectrode. Lower magnitudes of k(s) and k(app)(0) imply that electrochemical reactions across the ITO-SLB electrodes are kinetically limited and consequently governed by electron tunneling across the SLBs. Standard theoretical rate constants (k(th)(0)) accrued upon electron tunneling comply with the potential-independent electron-tunneling coefficient β = 0.15 Å(-1). Insulator-semiconductor transitions moving from a liquid-expanded to a condensed 2D-phase state of the SLBs are noted, adding a new dimension to their transport behavior. These results highlight the role of tryptophan in expediting electron transfer across lipid bilayer membranes in a cellular environment and can provide potential clues towards patterned lipid nanocomposites and devices. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Drug release from and hydrolytic degradation of a poly(ethylene glycol) grafted poly(3-hydroxyoctanoate).

PubMed

Kim, Hyung Woo; Chung, Chung Wook; Hwang, Sung Joo; Rhee, Young Ha

2005-07-01

Monoacrylate-poly(ethylene glycol)-grafted poly(3-hydroxyoctanoate) (PEGMA-g-PHO) copolymers were synthesized to develop a swelling-controlled release delivery system for ibuprofen as a model drug. The in vitro hydrolytic degradation of and the drug release from a film made of the PEGMA-g-PHO copolymer were carried out in a phosphate buffer saline (pH 7.4) medium. The hydrolytic degradation of the copolymer was strongly dependent on the degree of grafting (DG) of the PEGMA group. The degradation rate of the copolymer films in vitro increased with increasing DG of the PEGMA group on the PHO chain. The copolymer films showed a controlled delivery of ibuprofen to the medium in periods of time that depend on the composition, hydrophilic/hydrophobic characteristics, initial drug loading amount and film thickness of the graft copolymer support. The drug release rate from the grafted copolymer films was faster than the rate of weight loss of the films themselves. In particular, a combination of the low DG of the PEGMA group in the PHO chains with the low ibuprofen solubility in water led to long-term constant release from these matrices in vitro.

Interactions of high-affinity cationic blockers with the translocation pores of B. anthracis, C. botulinum, and C. perfringens binary toxins.

PubMed

Bezrukov, Sergey M; Liu, Xian; Karginov, Vladimir A; Wein, Alexander N; Leppla, Stephen H; Popoff, Michel R; Barth, Holger; Nestorovich, Ekaterina M

2012-09-19

Cationic β-cyclodextrin derivatives were recently introduced as highly effective, potentially universal blockers of three binary bacterial toxins: anthrax toxin of Bacillus anthracis, C2 toxin of Clostridium botulinum, and iota toxin of Clostridium perfringens. The binary toxins are made of two separate components: the enzymatic A component, which acts on certain intracellular targets, and the binding/translocation B component, which forms oligomeric channels in the target cell membrane. Here we studied the voltage and salt dependence of the rate constants of binding and dissociation reactions of two structurally different β-cyclodextrins (AmPrβCD and AMBnTβCD) in the PA(63), C2IIa, and Ib channels (B components of anthrax, C2, and iota toxins, respectively). With all three channels, the blocker carrying extra hydrophobic aromatic groups on the thio-alkyl linkers of positively charged amino groups, AMBnTβCD, demonstrated significantly stronger binding compared with AmPrβCD. This effect is seen as an increased residence time of the blocker in the channels, whereas the time between blockages characterizing the binding reaction on-rate stays practically unchanged. Surprisingly, the voltage sensitivity, expressed as a slope of the logarithm of the blocker residence time as a function of voltage, turned out to be practically the same for all six cases studied, suggesting structural similarities among the three channels. Also, the more-effective AMBnTβCD blocker shows weaker salt dependence of the binding and dissociation rate constants compared with AmPrβCD. By estimating the relative contributions of the applied transmembrane field, long-range Coulomb, and salt-concentration-independent, short-range forces, we found that the latter represent the leading interaction, which accounts for the high efficiency of blockage. In a search for the putative groups in the channel lumen that are responsible for the short-range forces, we performed measurements with the F427A mutant of PA(63), which lacks the functionally important phenylalanine clamp. We found that the on-rates of the blockage were virtually conserved, but the residence times and, correspondingly, the binding constants dropped by more than an order of magnitude, which also reduced the difference between the efficiencies of the two blockers. Copyright © 2012 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Effect of substitution group on dielectric properties of 4H-pyrano [3, 2-c] quinoline derivatives thin films

NASA Astrophysics Data System (ADS)

H, M. Zeyada; F, M. El-Taweel; M, M. El-Nahass; M, M. El-Shabaan

2016-07-01

The AC electrical conductivity and dielectrical properties of 2-amino-6-ethyl-5-oxo-4-(3-phenoxyphenyl)-5,6-dihydro-4H-pyrano[3, 2-c]quinoline-3-carbonitrile (Ph-HPQ) and 2-amino-4-(2-chlorophenyl)-6-ethyl-5-oxo-5,6-dihydro-4H-pyrano [3, 2-c] quinoline-3-carbonitrile (Ch-HPQ) thin films were determined in the frequency range of 0.5 kHz-5 MHz and the temperature range of 290-443 K. The AC electrical conduction of both compounds in thin film form is governed by the correlated barrier hopping (CBH) mechanism. Some parameters such as the barrier height, the maximum barrier height, the density of charges, and the hopping distance were determined as functions of temperature and frequency. The phenoxyphenyl group has a greater influence on those parameters than the chlorophenyl group. The AC activation energies were determined at different frequencies and temperatures. The dielectric behaviors of Ph-HPQ and Ch-HPQ were investigated using the impedance spectroscopy technique. The impedance data are presented in Nyquist diagrams for different temperatures. The Ch-HPQ films have higher impedance than the Ph-HPQ films. The real dielectric constant and dielectric loss show a remarkable dependence on the frequency and temperature. The Ph-HPQ has higher dielectric constants than the Ch-HPQ.

Calculation of individual isotope equilibrium constants for geochemical reactions

USGS Publications Warehouse

Thorstenson, D.C.; Parkhurst, D.L.

2004-01-01

Theory is derived from the work of Urey (Urey H. C. [1947] The thermodynamic properties of isotopic substances. J. Chem. Soc. 562-581) to calculate equilibrium constants commonly used in geochemical equilibrium and reaction-transport models for reactions of individual isotopic species. Urey showed that equilibrium constants of isotope exchange reactions for molecules that contain two or more atoms of the same element in equivalent positions are related to isotope fractionation factors by ?? = (Kex)1/n, where n is the number of atoms exchanged. This relation is extended to include species containing multiple isotopes, for example 13C16O18O and 1H2H18O. The equilibrium constants of the isotope exchange reactions can be expressed as ratios of individual isotope equilibrium constants for geochemical reactions. Knowledge of the equilibrium constant for the dominant isotopic species can then be used to calculate the individual isotope equilibrium constants. Individual isotope equilibrium constants are calculated for the reaction CO2g = CO2aq for all species that can be formed from 12C, 13C, 16O, and 18O; for the reaction between 12C18 O2aq and 1H218Ol; and among the various 1H, 2H, 16O, and 18O species of H2O. This is a subset of a larger number of equilibrium constants calculated elsewhere (Thorstenson D. C. and Parkhurst D. L. [2002] Calculation of individual isotope equilibrium constants for implementation in geochemical models. Water-Resources Investigation Report 02-4172. U.S. Geological Survey). Activity coefficients, activity-concentration conventions for the isotopic variants of H2O in the solvent 1H216Ol, and salt effects on isotope fractionation have been included in the derivations. The effects of nonideality are small because of the chemical similarity of different isotopic species of the same molecule or ion. The temperature dependence of the individual isotope equilibrium constants can be calculated from the temperature dependence of the fractionation factors. The derivations can be extended to calculation of individual isotope equilibrium constants for ion pairs and equilibrium constants for isotopic species of other chemical elements. The individual isotope approach calculates the same phase isotopic compositions as existing methods, but also provides concentrations of individual species, which are needed in calculations of mass-dependent effects in transport processes. The equilibrium constants derived in this paper are used to calculate the example of gas-water equilibrium for CO2 in an acidic aqueous solution. ?? 2004 Elsevier Ltd.

Vicinal 1H-1H NMR coupling constants from density functional theory as reliable tools for stereochemical analysis of highly flexible multichiral center molecules.

PubMed

López-Vallejo, Fabian; Fragoso-Serrano, Mabel; Suárez-Ortiz, Gloria Alejandra; Hernández-Rojas, Adriana C; Cerda-García-Rojas, Carlos M; Pereda-Miranda, Rogelio

2011-08-05

A protocol for stereochemical analysis, based on the systematic comparison between theoretical and experimental vicinal (1)H-(1)H NMR coupling constants, was developed and applied to a series of flexible compounds (1-8) derived from the 6-heptenyl-5,6-dihydro-2H-pyran-2-one framework. The method included a broad conformational search, followed by geometry optimization at the DFT B3LYP/DGDZVP level, calculation of the vibrational frequencies, thermochemical parameters, magnetic shielding tensors, and the total NMR spin-spin coupling constants. Three scaling factors, depending on the carbon atom hybridizations, were found for the (1)H-C-C-(1)H vicinal coupling constants: f((sp3)-(sp3)) = 0.910, f((sp3)-(sp2)) = 0.929, and f((sp2)-(sp2))= 0.977. A remarkable correlation between the theoretical (J(pre)) and experimental (1)H-(1)H NMR (J(exp)) coupling constants for spicigerolide (1), a cytotoxic natural product, and some of its synthetic stereoisomers (2-4) demonstrated the predictive value of this approach for the stereochemical assignment of highly flexible compounds containing multiple chiral centers. The stereochemistry of two natural 6-heptenyl-5,6-dihydro-2H-pyran-2-ones (14 and 15) containing diverse functional groups in the heptenyl side chain was also analyzed by application of this combined theoretical and experimental approach, confirming its reliability. Additionally, a geometrical analysis for the conformations of 1-8 revealed that weak hydrogen bonds substantially guide the conformational behavior of the tetraacyloxy-6-heptenyl-2H-pyran-2-ones.

The VO(2)-on kinetics in constant load exercise sub-anaerobic threshold reflects endothelial function and dysfunction in muscle microcirculation.

PubMed

Maione, D; Cicero, A Fg; Bacchelli, S; Cosentino, E R; Degli Esposti, D; Manners, D N; Rinaldi, E R; Rosticci, M; Senaldi, R; Ambrosioni, E; Borghi, C

2015-01-01

To propose a test to evaluate endothelial function, based on VO(2) on-transition kinetics in sub-anaerobic threshold (AT) constant load exercise, we tested healthy subjects and patients with ischemic-hypertensive cardiopathy by two cardiopulmonary tests on a cycle ergometer endowed with an electric motor to overcome initial inertia: a pre-test and, after at least 24 h, one 6 min constant load exercise at 90 % AT. We measured net phase 3 VO(2)-on kinetics and, by phase 2 time constant (tau), valued endothelial dysfunction. We found shorter tau in repeated tests, shorter time between first and second test, by persisting endothelium-dependent arteriolar vasodilatation and/or several other mechanisms. Reducing load to 80 % and 90 % AT did not produce significant changes in tau of healthy volunteers, while in heart patients an AT load of 70 %, compared to 80 % AT, shortened tau (delta=4.38+/-1.65 s, p=0.013). In heart patients, no correlation was found between NYHA class, ejection fraction (EF), and the two variables derived from incremental cycle cardio-pulmonary exercise, as well as between EF and tau; while NYHA class groups were well correlated with tau duration (r=0.92, p=0.0001). Doxazosin and tadalafil also significantly reduced tau. In conclusion, the O(2) consumption kinetics during the on-transition of constant load exercise below the anaerobic threshold are highly sensitive to endothelial function in muscular microcirculation, and constitute a marker for the evaluation of endothelial dysfunction.

Disparate effects of constant and annually-cycling daylength and water temperature on reproductive maturation of striped bass (Morone saxatilis)

USGS Publications Warehouse

Clark, R.W.; Henderson-Arzapalo, A.; Sullivan, C.V.

2005-01-01

Adult striped bass (Morone saxatilis) were exposed to various combinations of constant or anually-cycling daylength and water temperature. Constant conditions (15 h days, 18??C) were those normally experienced at spawning and cycling conditions simulated natural changes at Chesapeake Bay latitude. Females exposed to constant long (15 h) days and cycling water temperature (TEMPERATURE group) had blood plasma levels of sex steroids (testosterone [T] and estradiol-17?? [E2]) and vitellogenin (Vg), and profiles of oocyte growth, that were nearly identical to those of females held under a natural photothermal cycle (CONTROL group). Several fish from these two groups were induced to spawn fertile eggs. Females constantly exposed to warm water (18??C), with or without a natural photoperiod cycle (PHOTOPERIOD and STATIC groups, respectively), had diminished circulating levels of gonadal steroid hormones and Vg, impaired deposition of yolk granules in their ooplasm, and decreased oocyte growth, and they underwent premature ovarian atresia. Males exposed to cycling water temperature (CONTROL and TEMPERATURE groups) spermiated synchronously during the natural breeding season, at which time they also had had high plasma androgen (T and 11-ketotestosterone [11-KT]) levels. The timing of spermiation was highly asynchronous among males in groups of fish held constantly at 18??C (STATIC and PHOTOPERIOD groups) and this asynchrony was associated with diminished plasma androgen levels. Termination of spermiation by males exposed to cycling water temperature coincided with a sharp decline in levels of plasma androgens about a month after water temperature rose above 18??C. In contrast, most males held constantly at 18??C sustained intermediate levels of plasma androgens and spermiated until the end of the study in late July. The annual cycle of water temperature clearly plays a prominent role in the initiation, maintenance, and termination of the striped bass reproductive cycle. In females, a decrease in water temperature below values experienced at spawning appears to be required for vitellogenesis and oocyte growth to proceed normally. Constant exposure of males to spawning temperature disrupts synchronous spermiation but also delays testicular regression, which may be useful for spawning fish after the natural reproductive season.

Characteristic effects of substituent and external pressure on group-inclusion complexation with p-sulfonatocalix[8]arene and γ-cyclodextrin

NASA Astrophysics Data System (ADS)

Miyazono, Keitaro; Hanaya, Tadashi; Sueishi, Yoshimi

2014-07-01

By synthesizing unique nitroxide probes (α-substituted phenyl-2,4,6-trimethoxybenzyl(t-butyl)nitroxide), we have shown that p-sulfonatocalix[8]arene (Calix-S8) and γ-cyclodextin (γ-CD) form electron spin resonance spectroscopically separable group-inclusion complexes (α-substituted phenyl-in (R-in) and t-butyl-in complexes) and determined the group-inclusion constants of Calix-S8 and γ-CD. Using nitroxide probes, we have examined the effects of substituent and external pressure on group-inclusion complexation with Calix-S8 and γ-CD. Experiments on pressure dependence enabled us to calculate the reaction volume (Δ V) for R-in and t-butyl-in complex formations. Δ V for group-in complexation with Calix-S8 had negative values. In contrast, Δ V values for γ-CD showed positive values, which is responsible for the repelled water molecules in the CD cavity. The characteristic pressure effects on group-in complexation suggest that group recognition by γ-CD is sensitive when compared with that by Calix-S8.

Parametric Methods for Determining the Characteristics of Long-Term Metal Strength

NASA Astrophysics Data System (ADS)

Nikitin, V. I.; Rybnikov, A. I.

2018-06-01

A large number of parametric methods were proposed to calculate the characteristics of the long-term strength of metals. All of them are based on the fact that temperature and time are mutually compensating factors in the processes of metal degradation at high temperature under the action of a constant stress. The analysis of the well-known Larson-Miller, Dorn-Shcherby, Menson-Haferd, Graham-Wallace, and Trunin parametric equations is performed. The widely used Larson-Miller parameter was subjected to a detailed analysis. The application of this parameter to the calculation of ultimate long-term strength for steels and alloys is substantiated provided that the laws of exponential dependence on temperature and power dependence on strength for the heat resistance are observed. It is established that the coefficient C in the Larson- Miller equation is a characteristic of the heat resistance and is different for each material. Therefore, the use of a universal constant C = 20 in parametric calculations, as well as an a priori presetting of numerical C values for each individual group of materials, is unacceptable. It is shown in what manner it is possible to determine an exact value of coefficient C for any material of interest as well as to obtain coefficient C depending on stress in case such a dependence is manifested. At present, the calculation of long-term strength characteristics can be performed to a sufficient accuracy using Larson-Miller's parameter and its refinements described therein as well as on the condition that a linear law in logσ- P dependence is observed and calculations in the interpolation range is performed. The use of the presented recommendations makes it possible to obtain a linear parametric logσ- P dependence, which makes it possible to determine to a sufficient accuracy the values of ultimate long-term strength for different materials.

Simultaneous estimation of intracellular free Mg2+ and pH by use of a new pH-dependent dissociation constant of MgATP.

PubMed

Nakayama, Shinsuke; Nomura, Hideki; Smith, Lorraine M; Clark, Joseph F

2002-06-01

In the present technical note for 31P-NMR, we used a new pH-dependent dissociation constant of MgATP, and re-estimated changes in the intracellular free Mg2+ concentration and pH from the chemical shifts of beta- and gamma-ATP during Na+-removal in smooth muscle. We confirmed the role of Na+ - Mg2+ exchange.

Temperature dependence of Henry's law constants and KOA for simple and heteroatom-substituted PAHs by COSMO-RS

NASA Astrophysics Data System (ADS)

Parnis, J. Mark; Mackay, Donald; Harner, Tom

2015-06-01

Henry's Law constants (H) and octanol-air partition coefficients (KOA) for polycyclic aromatic hydrocarbons (PAHs) and selected nitrogen-, oxygen- and sulfur-containing derivatives have been computed using the COSMO-RS method between -5 and 40 °C in 5 °C intervals. The accuracy of the estimation was assessed by comparison of COSMOtherm values with published experimental temperature-dependence data for these and similar PAHs. COSMOtherm log H estimates with temperature-variation for parent PAHs are shown to have a root-mean-square (RMS) error of 0.38 (PAH), based on available validation data. Estimates of O-, N- and S-substituted derivative log H values are found to have RMS errors of 0.30 at 25 °C. Log KOA estimates with temperature variation from COSMOtherm are shown to be strongly correlated with experimental values for a small set of unsubstituted PAHs, but with a systematic underestimation and associated RMS error of 1.11. Similar RMS error of 1.64 was found for COSMO-RS estimates of a group of critically-evaluated log KOA values at room temperature. Validation demonstrates that COSMOtherm estimates of H and KOA are of sufficient accuracy to be used for property screening and preliminary environmental risk assessment, and perform very well for modeling the influence of temperature on partitioning behavior in the temperature range -5 to 40 °C. Temperature-dependent shifts of up to 2 log units in log H and one log unit for log KOA are predicted for PAH species over the range -5 and 40 °C. Within the family of PAH molecules, COSMO-RS is sufficiently accurate to make it useful as a source of estimates for modeling purposes, following corrections for systematic underestimation of KOA. Average changes in the values for log H and log KOA upon substitution are given for various PAH substituent categories, with the most significant shifts being associated with the ionizing nitro functionality and keto groups.

Concentration dependence of molal conductivity and dielectric constant of 1-alcohol electrolytes using the compensated arrhenius formalism.

PubMed

Fleshman, Allison M; Petrowsky, Matt; Frech, Roger

2013-05-02

The molal conductivity of liquid electrolytes with low static dielectric constants (ε(s) < 10) decreases to a minimum at low concentrations (region I) and increases to a maximum at higher concentrations (region II) when plotted against the square root of the concentration. This behavior is investigated by applying the compensated Arrhenius formalism (CAF) to the molal conductivity, Λ, of a family of 1-alcohol electrolytes over a broad concentration range. A scaling procedure is applied that results in an energy of activation (E(a)) and an exponential prefactor (Λ0) that are both concentration dependent. It is shown that the increasing molal conductivity in region II results from the combined effect of (1) a decrease in the energy of activation calculated from the CAF, and (2) an inherent concentration dependence in the exponential prefactor that is partly due to the dielectric constant.

Temperature-dependent ac conductivity and dielectric response of vanadium doped CaCu3Ti4O12 ceramic

NASA Astrophysics Data System (ADS)

Sen, A.; Maiti, U. N.; Thapa, R.; Chattopadhyay, K. K.

2011-09-01

Successful incorporation of vanadium dopant within the giant dielectric material CaCu 3Ti 4O12 (CCTO) through a conventional solid-state sintering process is achieved and its influence on the dielectric as well as electrical properties as a function of temperature and frequency is reported here. Proper crystalline phase formation together with dopant induced lattice constant shrinkage was confirmed through X-ray diffraction. The temperature dependence of the dielectric constant at different constant frequencies was investigated. We infer that the correlated barrier hopping (CBH) model is dominant in the conduction mechanism of the ceramic as per the temperature-dependent ac conductivity measurements. The electronic parameters such as density of the states at the Fermi level, N( E f) and hopping distance, R ω of the ceramic were also calculated using this model.

Compensation of Verdet Constant Temperature Dependence by Crystal Core Temperature Measurement

PubMed Central

Petricevic, Slobodan J.; Mihailovic, Pedja M.

2016-01-01

Compensation of the temperature dependence of the Verdet constant in a polarimetric extrinsic Faraday sensor is of major importance for applying the magneto-optical effect to AC current measurements and magnetic field sensing. This paper presents a method for compensating the temperature effect on the Faraday rotation in a Bi12GeO20 crystal by sensing its optical activity effect on the polarization of a light beam. The method measures the temperature of the same volume of crystal that effects the beam polarization in a magnetic field or current sensing process. This eliminates the effect of temperature difference found in other indirect temperature compensation methods, thus allowing more accurate temperature compensation for the temperature dependence of the Verdet constant. The method does not require additional changes to an existing Δ/Σ configuration and is thus applicable for improving the performance of existing sensing devices. PMID:27706043

Diffusion of neon in white dwarf stars.

PubMed

Hughto, J; Schneider, A S; Horowitz, C J; Berry, D K

2010-12-01

Sedimentation of the neutron rich isotope 22Ne may be an important source of gravitational energy during the cooling of white dwarf stars. This depends on the diffusion constant for 22Ne in strongly coupled plasma mixtures. We calculate self-diffusion constants D(i) from molecular dynamics simulations of carbon, oxygen, and neon mixtures. We find that D(i) in a mixture does not differ greatly from earlier one component plasma results. For strong coupling (coulomb parameter Γ> few), D(i) has a modest dependence on the charge Z(i) of the ion species, D(i)∝Z(i)(-2/3). However, D(i) depends more strongly on Z(i) for weak coupling (smaller Γ). We conclude that the self-diffusion constant D(Ne) for 22Ne in carbon, oxygen, and neon plasma mixtures is accurately known so that uncertainties in D(Ne) should be unimportant for simulations of white dwarf cooling.

Effects of egg incubation condition on the post-hatching growth and performance of the snapping turtle, Chelydra serpentina

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ryan, Kathleen M.

1990-12-01

The effect of incubation temperature on the post-hatching growth and performance capacities of the common snapping turtle, Chelydra serpentina was investigated in the laboratory. Turtle eggs were collected from four sites in New York State and randomly assigned to four incubation temperature treatments to produce males (constant 26°C and downshifted 30-26-30°C) and females (constant 30°C and upshifted 26-30-26°C) under constant and altered temperature regimes. The incubation conditions resulted in 92% males from the constant 26°C group and 93% males from the downshifted group. 100% females resulted from both the constant 30°C group and the upshifted group. Turtles hatching from eggsmore » incubated constantly at 26°C were significantly larger than hatchlings from eggs incubated at a constant 30°C or downshifted. Hatchlings were raised in individual aquaria at 25°C and fed earthworms and fish. After a 9-month growth period, turtles which had been incubated at a constant 30°C gained significantly more mass than did turtles from eggs which had been downshifted or upshifted. There was no extended effect of incubation condition on Post-hatching performance and learning ability as measured by righting and feeding responses. Thus, the mass gain differences seen in this study suggest that physiological differences do result as the consequence of incubation condition. However, these physiological differences are not reflected in normal locomotive or feeding behavior.« less

Effects of egg incubation condition on the post-hatching growth and performance of the snapping turtle, Chelydra serpentina

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ryan, K.M.

1990-12-01

The effect of incubation temperature on the post-hatching growth and performance capacities of the common snapping turtle, Chelydra serpentina was investigated in the laboratory. Turtle eggs were collected from four sites in New York State and randomly assigned to four incubation temperature treatments to produce males (constant 26[degree]C and downshifted 30-26-30[degree]C) and females (constant 30[degree]C and upshifted 26-30-26[degree]C) under constant and altered temperature regimes. The incubation conditions resulted in 92% males from the constant 26[degree]C group and 93% males from the downshifted group. 100% females resulted from both the constant 30[degree]C group and the upshifted group. Turtles hatching from eggsmore » incubated constantly at 26[degree]C were significantly larger than hatchlings from eggs incubated at a constant 30[degree]C or downshifted. Hatchlings were raised in individual aquaria at 25[degree]C and fed earthworms and fish. After a 9-month growth period, turtles which had been incubated at a constant 30[degree]C gained significantly more mass than did turtles from eggs which had been downshifted or upshifted. There was no extended effect of incubation condition on Post-hatching performance and learning ability as measured by righting and feeding responses. Thus, the mass gain differences seen in this study suggest that physiological differences do result as the consequence of incubation condition. However, these physiological differences are not reflected in normal locomotive or feeding behavior.« less

[Quantitative study of the prothallial morphogenesis in Asplenium species].

PubMed

Henriet, M; Auquière, J P; Moens, P

1976-01-01

A precedent paper concerned a qualitative analysis of the gametophytic development in nine Asplenium species. By a quantitative study, we specify the parental relationships among these species. The surface of the gametophyte and the number of maginal hairs increase differently for each species. The density of the marginal hairs depends on the considered species. The relation among the morphological gametophytic parameters is constant in a group of determined species. The principal componant analysis is realized for all the parameters measured during the prothallial development. It confirms parental relationships among the diploids and tetraploids species on a morphological point of vue.

Self-dual monopoles and toda molecules

NASA Astrophysics Data System (ADS)

Ganoulis, N.; Goddard, P.; Olive, D.

1982-07-01

Stable static solutions to a gauge field theory with a Higgs field in the adjoint representation and with vanishing self-coupling are self-dual in the sense of Bogomolny. Leznov and Saveliev showed that a specific form of spherical symmetry reduces these equations to a modified form of the Toda molecule equations associated with the overall gauge symmetry G. Values of the constants of integration are found in terms of the distant Higgs field, guaranteeing regularity of the solution at the origin. The expressions hold for any simple Lie group G, depending on G via its root system.

Elastic response of binary hard-sphere fluids

NASA Astrophysics Data System (ADS)

Rickman, J. M.; Ou-Yang, H. Daniel

2011-07-01

We derive expressions for the high-frequency, wave-number-dependent elastic constants of a binary hard-sphere fluid and employ Monte Carlo computer simulation to evaluate these constants in order to highlight the impact of composition and relative sphere diameter on the elastic response of this system. It is found that the elastic constant c11(k) exhibits oscillatory behavior as a function of k whereas the high-frequency shear modulus, for example, does not. This behavior is shown to be dictated by the angular dependence (in k⃗ space) of derivatives of the interatomic force at contact. The results are related to recent measurements of the compressibility of colloidal fluids in laser trapping experiments.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen Lin; Chen Yixin

We show that no universal quantum cloning machine exists that can broadcast an arbitrary mixed qubit with a constant fidelity. Based on this result, we investigate the dependent quantum cloner in the sense that some parameter of the input qubit {rho}{sub s}({theta},{omega},{lambda}) is regarded as constant in the fidelity. For the case of constant {omega}, we establish the 1{yields}2 optimal symmetric dependent cloner with a fidelity 1/2. It is also shown that the 1{yields}M optimal quantum cloning machine for pure qubits is also optimal for mixed qubits, when {lambda} is the unique parameter in the fidelity. For general N{yields}M broadcastingmore » of mixed qubits, the situation is very different.« less

Carbon Nanotube Oscillator Surface Profiling Device and Method of Use

DTIC Science & Technology

2011-11-15

distance p. The constants A and B are the Hamaker constants, which depend on the materials of the two interacting bodies. The total vdW inter...wall CNT 45 with 2L1 =2L2 =150 A and a sample of specific material char- acterized with atomic density a, Hamaker constants A and B, and a friction

Soliton solutions, stability analysis and conservation laws for the brusselator reaction diffusion model with time- and constant-dependent coefficients

NASA Astrophysics Data System (ADS)

Inc, Mustafa; Yusuf, Abdullahi; Isa Aliyu, Aliyu; Hashemi, M. S.

2018-05-01

This paper studies the brusselator reaction diffusion model (BRDM) with time- and constant-dependent coefficients. The soliton solutions for BRDM with time-dependent coefficients are obtained via first integral (FIM), ansatz, and sine-Gordon expansion (SGEM) methods. Moreover, it is well known that stability analysis (SA), symmetry analysis and conservation laws (CLs) give several information for modelling a system of differential equations (SDE). This is because they can be used for investigating the internal properties, existence, uniqueness and integrability of different SDE. For this reason, we investigate the SA via linear stability technique, symmetry analysis and CLs for BRDM with constant-dependent coefficients in order to extract more physics and information on the governing equation. The constraint conditions for the existence of the solutions are also examined. The new solutions obtained in this paper can be useful for describing the concentrations of diffusion problems of the BRDM. It is shown that the examined dependent coefficients are some of the factors that are affecting the diffusion rate. So, the present paper provides much motivational information in comparison to the existing results in the literature.

A nonmonotonic dependence of standard rate constant on reorganization energy for heterogeneous electron transfer processes on electrode surface

NASA Astrophysics Data System (ADS)

Xu, Weilin; Li, Songtao; Zhou, Xiaochun; Xing, Wei; Huang, Mingyou; Lu, Tianhong; Liu, Changpeng

2006-05-01

In the present work a nonmonotonic dependence of standard rate constant (k0) on reorganization energy (λ) was discovered qualitatively from electron transfer (Marcus-Hush-Levich) theory for heterogeneous electron transfer processes on electrode surface. It was found that the nonmonotonic dependence of k0 on λ is another result, besides the disappearance of the famous Marcus inverted region, coming from the continuum of electronic states in electrode: with the increase of λ, the states for both Process I and Process II ET processes all vary from nonadiabatic to adiabatic state continuously, and the λ dependence of k0 for Process I is monotonic thoroughly, while for Process II on electrode surface the λ dependence of k0 could show a nonmonotonicity.

The anisotropic Hooke's law for cancellous bone and wood.

PubMed

Yang, G; Kabel, J; van Rietbergen, B; Odgaard, A; Huiskes, R; Cowin, S C

A method of data analysis for a set of elastic constant measurements is applied to data bases for wood and cancellous bone. For these materials the identification of the type of elastic symmetry is complicated by the variable composition of the material. The data analysis method permits the identification of the type of elastic symmetry to be accomplished independent of the examination of the variable composition. This method of analysis may be applied to any set of elastic constant measurements, but is illustrated here by application to hardwoods and softwoods, and to an extraordinary data base of cancellous bone elastic constants. The solid volume fraction or bulk density is the compositional variable for the elastic constants of these natural materials. The final results are the solid volume fraction dependent orthotropic Hooke's law for cancellous bone and a bulk density dependent one for hardwoods and softwoods.

Re/Os constraint on the time variability of the fine-structure constant.

PubMed

Fujii, Yasunori; Iwamoto, Akira

2003-12-31

We argue that the accuracy by which the isochron parameters of the decay 187Re-->187Os are determined by dating iron meteorites may constrain the possible time dependence of the decay rate and hence of the fine-structure constant alpha, not directly but only in a model-dependent manner. From this point of view, some of the attempts to analyze the Oklo constraint and the results of the quasistellar-object absorption lines are reexamined.

Functional dependence of resonant harmonics on nanomechanical parameters in dynamic mode atomic force microscopy.

PubMed

Gramazio, Federico; Lorenzoni, Matteo; Pérez-Murano, Francesc; Rull Trinidad, Enrique; Staufer, Urs; Fraxedas, Jordi

2017-01-01

We present a combined theoretical and experimental study of the dependence of resonant higher harmonics of rectangular cantilevers of an atomic force microscope (AFM) as a function of relevant parameters such as the cantilever force constant, tip radius and free oscillation amplitude as well as the stiffness of the sample's surface. The simulations reveal a universal functional dependence of the amplitude of the 6th harmonic (in resonance with the 2nd flexural mode) on these parameters, which can be expressed in terms of a gun-shaped function. This analytical expression can be regarded as a practical tool for extracting qualitative information from AFM measurements and it can be extended to any resonant harmonics. The experiments confirm the predicted dependence in the explored 3-45 N/m force constant range and 2-345 GPa sample's stiffness range. For force constants around 25 N/m, the amplitude of the 6th harmonic exhibits the largest sensitivity for ultrasharp tips (tip radius below 10 nm) and polymers (Young's modulus below 20 GPa).

(Ba+Sr)/Ti ratio dependence of the dielectric properties for (Ba0.5Sr0.5)TiO3 thin films prepared by ion beam sputtering

NASA Astrophysics Data System (ADS)

Yamamichi, Shintaro; Yabuta, Hisato; Sakuma, Toshiyuki; Miyasaka, Yoichi

1994-03-01

(Ba0.5Sr0.5)TiO3 thin films were prepared by ion beam sputtering from powder targets with (Ba+Sr)/Ti ratios ranging from 0.80 to 1.50. All of the perovskite (Ba,Sr)TiO3 films were single phase except for the film with a (Ba+Sr)/Ti ratio of 1.41. The dielectric constant values notably depended on the (Ba+Sr)/Ti ratio for films thicker than 70 nm. The highest dielectric constant of 580 was achieved for the 5% (Ba+Sr) rich film. This (Ba+Sr)/Ti ratio dependence was diminished by the thickness dependence for thinner films. The grain sizes for the 9% (Ba+Sr) rich film and for the 6% (Ba+Sr) poor film ranged from 70 to 100 nm and from 30 to 60 nm, respectively. This grain size difference could explain why slightly A-site rich (Ba,Sr)TiO3 films have a larger dielectric constant than A-site poor films.

Effect of soil texture on the microwave emission from soils

NASA Technical Reports Server (NTRS)

Schmugge, T. J.

1980-01-01

The intensity brightness temperature of the microwave emission from the soil is determined primarily by its dielectric properties. The large difference between the dielectric constant of water and that of dry soil produces a strong dependence of the soil's dielectric constant on its moisture content. This dependence is effected by the texture of the soil because the water molecules close to the particle surface are tightly bound and do not contribute significantly to the dielectric properties. Since this surface area is a function of the particle size distribution (soil texture), being larger for clay soils with small particles, and smaller for sandy soils with larger particles; the dielectric properties will depend on soil texture. Laboratory measurements of the dielectric constant for soils are summarized. The dependence of the microwave emission on texture is demonstrated by measurements of brightness temperature from an aircraft platform for a wide range of soil textures. It is concluded that the effect of soil texture differences on the observed values can be normalized by expressing the soil moisture values as a percent field capacity for the soil.

Rate dependent deformation of porous sandstone across the brittle-ductile transition

NASA Astrophysics Data System (ADS)

Jefferd, M.; Brantut, N.; Mitchell, T. M.; Meredith, P. G.

2017-12-01

Porous sandstones transition from dilatant, brittle deformation at low pressure, to compactant, ductile deformation at high pressure. Both deformation modes are driven by microcracking, and are expected to exhibit a time dependency due to chemical interactions between the pore fluid and the rock matrix. In the brittle regime, time-dependent failure and brittle creep are well documented. However, much less is understood in the ductile regime. We present results from a series of triaxial deformation experiments, performed in the brittle-ductile transition zone of fluid saturated Bleurswiller sandstone (initial porosity = 23%). Samples were deformed at 40 MPa effective pressure, to 4% axial strain, under either constant strain rate (10-5 s-1) or constant stress (creep) conditions. In addition to stress, axial strain and pore volume change, P wave velocities and acoustic emission were monitored throughout. During constant stress tests, the strain rate initially decreased with increasing strain, before reaching a minimum and accelerating to a constant level beyond 2% axial strain. When plotted against axial strain, the strain rate evolution under constant stress conditions, mirrors the stress evolution during the constant strain rate tests; where strain hardening occurs prior to peak stress, which is followed by strain softening and an eventual plateau. In all our tests, the minimum strain rate during creep occurs at the same inelastic strain as the peak stress during constant strain tests, and strongly decreases with decreasing applied stress. The microstructural state of the rock, as interpreted from similar volumetric strain curves, as well as the P-wave velocity evolution and AE production rate, appears to be solely a function of the total inelastic strain, and is independent of the length of time required to reach said strain. We tested the sensitivity of fluid chemistry on the time dependency, through a series of experiments performed under similar stress conditions, but with chemically inert decane instead of water as the pore fluid. Under the same applied stress, decane saturated samples reached a minimum strain rate 2 orders of magnitude lower than the water saturated samples. This is consistent with a mechanism of subcritical crack growth driven by chemical interactions between the pore fluid and the rock.

Transverse relaxation in the rotating frame induced by chemical exchange.

PubMed

Michaeli, Shalom; Sorce, Dennis J; Idiyatullin, Djaudat; Ugurbil, Kamil; Garwood, Michael

2004-08-01

In the presence of radiofrequency irradiation, relaxation of magnetization aligned with the effective magnetic field is characterized by the time constant T1rho. On the other hand, the time constant T2rho characterizes the relaxation of magnetization that is perpendicular to the effective field. Here, it is shown that T2rho can be measured directly with Carr-Purcell sequences composed of a train of adiabatic full-passage (AFP) pulses. During adiabatic rotation, T2rho characterizes the relaxation of the magnetization, which under adiabatic conditions remains approximately perpendicular to the time-dependent effective field. Theory is derived to describe the influence of chemical exchange on T2rho relaxation in the fast-exchange regime, with time constant defined as T2rho,ex. The derived theory predicts the rate constant R2rho,ex (= 1/T2rho,ex) to be dependent on the choice of amplitude- and frequency-modulation functions used in the AFP pulses. Measurements of R2rho,ex of the water/ethanol exchanging system confirm the predicted dependence on modulation functions. The described theoretical framework and adiabatic methods represent new tools to probe exchanging systems. Copyright 2004 Elsevier Inc.

Arthroscopic removal of intraosseous and intratendinous deposits in calcifying tendinitis of the rotator cuff.

PubMed

Seyahi, Aksel; Demirhan, Mehmet

2009-06-01

The purpose of this study was to evaluate the surgical outcome of arthroscopic removal of intraosseous deposits in calcifying tendinitis of the rotator cuff. We studied the results of arthroscopic treatment in 30 shoulders in 28 patients with calcifying tendinitis (mean age, 48.3 years; age range, 26 to 83 years), with a mean follow-up of 38 months. According to the localization of calcification, the patients were divided into 2 groups: those with pure tendinous/soft-tissue involvement (n = 25) (group I) and those with tendinous/soft-tissue and osseous involvement (n = 5) (group II). After routine tendon debridement, debridement and curettage of the bone lesion were also performed in patients with bone involvement. Clinical outcome was evaluated by use of the pain score on a visual analog scale and the Constant score, and a special inquiry was used for self-assessment. The pain scores and functional Constant scores improved significantly after the operation in both groups (P = .043 for pain score and P = .0001 for Constant score in group I and P = .042 for pain score and P = .0001 for Constant score in group II). The median Constant score increased from 42 (range, 22 to 65) preoperatively to 100 (range, 80 to 100) postoperatively in group I and from 40 (range, 25 to 55) to 100 (range, 85 to 100) in group II. The mean pain score was 6.5 +/- 1.4 (range, 4 to 9) before treatment and 0.2 +/- 0.5 (range, 0 to 2) at follow-up in group I, and it was 6.2 +/- 1.48 (range, 4 to 8) and 0.4 +/- 0.55 (range, 0 to 1), respectively, in group II. There was no significant difference between the 2 groups in terms of the final Constant (P = .85) and pain scores (P = .26). Arthroscopic removal of intraosseous and intratendinous deposits to treat calcifying tendinitis with osseous involvement seems to be as safe and effective a treatment method as the arthroscopic removal of intratendinous deposits in cases of tendinous involvement only. Level IV, therapeutic case series.

Comparison of the acid-base properties of ribose and 2'-deoxyribose nucleotides.

PubMed

Mucha, Ariel; Knobloch, Bernd; Jezowska-Bojczuk, Małgorzata; Kozłowski, Henryk; Sigel, Roland K O

2008-01-01

The extent to which the replacement of a ribose unit by a 2'-deoxyribose unit influences the acid-base properties of nucleotides has not hitherto been determined in detail. In this study, by potentiometric pH titrations in aqueous solution, we have measured the acidity constants of the 5'-di- and 5'-triphosphates of 2'-deoxyguanosine [i.e., of H(2)(dGDP)(-) and H(2)(dGTP)(2-)] as well as of the 5'-mono-, 5'-di-, and 5'-triphosphates of 2'-deoxyadenosine [i.e., of H(2)(dAMP)(+/-), H(2)(dADP)(-), and H(2)(dATP)(2-)]. These 12 acidity constants (of the 56 that are listed) are compared with those of the corresponding ribose derivatives (published data) measured under the same experimental conditions. The results show that all protonation sites in the 2'-deoxynucleotides are more basic than those in their ribose counterparts. The influence of the 2'-OH group is dependent on the number of 5'-phosphate groups as well as on the nature of the purine nucleobase. The basicity of N7 in guanine nucleotides is most significantly enhanced (by about 0.2 pK units), while the effect on the phosphate groups and the N1H or N1H(+) sites is less pronounced but clearly present. In addition, (1)H NMR chemical shift change studies in dependence on pD in D(2)O have been carried out for the dAMP, dADP, and dATP systems, which confirmed the results from the potentiometric pH titrations and showed the nucleotides to be in their anti conformations. Overall, our results are not only of relevance for metal ion binding to nucleotides or nucleic acids, but also constitute an exact basis for the calculation, determination, and understanding of perturbed pK(a) values in DNAzymes and ribozymes, as needed for the delineation of acid-base mechanisms in catalysis.

Chimera States in Neural Oscillators

NASA Astrophysics Data System (ADS)

Bahar, Sonya; Glaze, Tera

2014-03-01

Chimera states have recently been explored both theoretically and experimentally, in various coupled nonlinear oscillators, ranging from phase-oscillator models to coupled chemical reactions. In a chimera state, both coherent and incoherent (or synchronized and desynchronized) states occur simultaneously in populations of identical oscillators. We investigate chimera behavior in a population of neural oscillators using the Huber-Braun model, a Hodgkin-Huxley-like model originally developed to characterize the temperature-dependent bursting behavior of mammalian cold receptors. One population of neurons is allowed to synchronize, with each neuron receiving input from all the others in its group (global within-group coupling). Subsequently, a second population of identical neurons is placed under an identical global within-group coupling, and the two populations are also coupled to each other (between-group coupling). For certain values of the coupling constants, the neurons in the two populations exhibit radically different synchronization behavior. We will discuss the range of chimera activity in the model, and discuss its implications for actual neural activity, such as unihemispheric sleep.

Induction of Metamorphosis Causes Differences in Sex-Specific Allocation Patterns in Axolotls (Ambystoma mexicanum) that Have Different Growth Histories.

PubMed

Clarkson, Pamela M; Beachy, Christopher K

2015-12-01

We tested the hypothesis that salamanders growing at different rates would have allocation patterns that differ among male and female metamorphic and larval salamanders. We raised individual axolotls, Ambystoma mexicanum , on four food regimes: constant high growth (throughout the experiment), constant low growth (restricted throughout the experiment), high growth switched to low growth (ad libitum switched after 140 d to restricted), and low growth switched to high growth (restricted switched after 140 d to ad libitum). Because axolotls are obligate paedomorphs, we exposed half of the salamanders to thyroid hormone to induce metamorphosis. We assayed growth and dissected and weighed gonads and fat bodies. Salamanders that were switched from restricted to ad libitum food regime delayed metamorphosis. In all treatment groups, females had larger gonads than males and males had larger fat bodies than females. The association between storage and reproduction differed between larvae and metamorphs and depended on sex.

Fitness to work of astronauts in conditions of action of the extreme emotional factors

NASA Astrophysics Data System (ADS)

Prisniakova, L. M.

2004-01-01

The theoretical model for the quantitative determination of influence of a level of emotional exertion on the success of human activity is presented. The learning curves of fixed words in the groups with a different level of the emotional exertion are analyzed. The obtained magnitudes of time constant T depending on a type of the emotional exertion are a quantitative measure of the emotional exertion. Time constants could also be of use for a prediction of the characteristic of fitness to work of an astronaut in conditions of extreme factors. The inverse of the sign of influencing on efficiency of activity of the man is detected. The paper offers a mathematical model of the relation between successful activity and motivations or the emotional exertion (Yerkes-Dodson law). Proposed models can serve by the theoretical basis of the quantitative characteristics of an estimation of activity of astronauts in conditions of the emotional factors at a phase of their selection.

Fitness to work of astronauts in conditions of action of the extreme emotional factors.

PubMed

Prisniakova, L M

2004-01-01

The theoretical model for the quantitative determination of influence of a level of emotional exertion on the success of human activity is presented. The learning curves of fixed words in the groups with a different level of the emotional exertion are analyzed. The obtained magnitudes of time constant T depending on a type of the emotional exertion are a quantitative measure of the emotional exertion. Time constants could also be of use for a prediction of the characteristic of fitness to work of an astronaut in conditions of extreme factors. The inverse of the sign of influencing on efficiency of activity of the man is detected. The paper offers a mathematical model of the relation between successful activity and motivations or the emotional exertion (Yerkes-Dodson law). Proposed models can serve by the theoretical basis of the quantitative characteristics of an estimation of activity of astronauts in conditions of the emotional factors at a phase of their selection. Published by Elsevier Ltd on behalf of COSPAR.

Degradation kinetics of gamma-oryzanol in antioxidant-stripped rice bran oil during thermal oxidation.

PubMed

Khuwijitjaru, Pramote; Yuenyong, Thippawan; Pongsawatmanit, Rungnaphar; Adachi, Shuji

2009-01-01

Gamma-oryzanol, a group of phytosterol ferulates found in rice bran, possesses antioxidative activity and other bioactivities. The kinetics of thermal degradation of gamma-oryzanol in stripped rice bran oil (SRBO) were investigated under heating at 132, 160, 192 and 222 degrees C for 480, 140, 60 and 50 h, respectively. Losses of the overall gamma-oryzanol and its components (cycloartenyl ferulate, 24-methylene cycloartanyl ferulate, campesteryl ferulate and beta-sitosteryl ferulate) could be expressed by the first-order kinetics model. The rate constant of thermal degradation of gamma-oryzanol increased with increasing heating temperatures. The temperature dependence of the obtained rate constants was found to obey the Arrhenius equation. Campesteryl ferulate showed slightly more thermally resistant than other components at temperature lower than 160 degrees C. However, the change in the absorbance from 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay as a function of heating time exhibited the same pattern for the SRBO with and without gamma-oryzanol for all studied heating temperatures.

Microscopic Modeling of Tribological Phenomena

DTIC Science & Technology

1990-02-28

37,4132 (1988). cohesive energy and lattice constant of nickel (t, -3.54 X 10- 󈧑 erg, ’This interface orientation was chosen in view ofour previous...such as lattice constants, heats of sublimation, elastic constants, vacancy-formation energies and heats of solution (47]. Following equilibration of...of the tip and 10 substrate materials to optimize their embedding energies (which are density dependent, deriving froam the tails of the atomic

Elastic and viscous properties of the nematic dimer CB7CB

NASA Astrophysics Data System (ADS)

Babakhanova, Greta; Parsouzi, Zeinab; Paladugu, Sathyanarayana; Wang, Hao; Nastishin, Yu. A.; Shiyanovskii, Sergij V.; Sprunt, Samuel; Lavrentovich, Oleg D.

2017-12-01

We present a comprehensive set of measurements of optical, dielectric, diamagnetic, elastic, and viscous properties in the nematic (N) phase formed by a liquid crystalline dimer. The studied dimer, 1,7-bis-4-(4'-cyanobiphenyl) heptane (CB7CB), is composed of two rigid rodlike cyanobiphenyl segments connected by a flexible aliphatic link with seven methyl groups. CB7CB and other nematic dimers are of interest due to their tendency to adopt bent configurations and to form two states possessing a modulated nematic director structure, namely, the twist-bend nematic, NTB, and the oblique helicoidal cholesteric, C hOH , which occurs when the achiral dimer is doped with a chiral additive and exposed to an external electric or magnetic field. We characterize the material parameters as functions of temperature in the entire temperature range of the N phase, including the pretransitional regions near the N -NTB and N-to-isotropic (I) transitions. The splay constant K11 is determined by two direct and independent techniques, namely, detection of the Frederiks transition and measurement of director fluctuation amplitudes by dynamic light scattering (DLS). The bend K33 and twist K22 constants are measured by DLS. K33, being the smallest of the three constants, shows a strong nonmonotonous temperature dependence with a negative slope in both N-I and N -NTB pretransitional regions. The measured ratio K11/K22 is larger than 2 in the entire nematic temperature range. The orientational viscosities associated with splay, twist, and bend fluctuations in the N phase are comparable to those of nematics formed by rodlike molecules. All three show strong temperature dependence, increasing sharply near the N -NTB transition.

Experimental and computational results on exciton/free-carrier ratio, hot/thermalized carrier diffusion, and linear/nonlinear rate constants affecting scintillator proportionality

NASA Astrophysics Data System (ADS)

Williams, R. T.; Grim, Joel Q.; Li, Qi; Ucer, K. B.; Bizarri, G. A.; Kerisit, S.; Gao, Fei; Bhattacharya, P.; Tupitsyn, E.; Rowe, E.; Buliga, V. M.; Burger, A.

2013-09-01

Models of nonproportional response in scintillators have highlighted the importance of parameters such as branching ratios, carrier thermalization times, diffusion, kinetic order of quenching, associated rate constants, and radius of the electron track. For example, the fraction ηeh of excitations that are free carriers versus excitons was shown by Payne and coworkers to have strong correlation with the shape of electron energy response curves from Compton-coincidence studies. Rate constants for nonlinear quenching are implicit in almost all models of nonproportionality, and some assumption about track radius must invariably be made if one is to relate linear energy deposition dE/dx to volume-based excitation density n (eh/cm3) in terms of which the rates are defined. Diffusion, affecting time-dependent track radius and thus density of excitations, has been implicated as an important factor in nonlinear light yield. Several groups have recently highlighted diffusion of hot electrons in addition to thermalized carriers and excitons in scintillators. However, experimental determination of many of these parameters in the insulating crystals used as scintillators has seemed difficult. Subpicosecond laser techniques including interband z scan light yield, fluence-dependent decay time, and transient optical absorption are now yielding experimental values for some of the missing rates and ratios needed for modeling scintillator response. First principles calculations and Monte Carlo simulations can fill in additional parameters still unavailable from experiment. As a result, quantitative modeling of scintillator electron energy response from independently determined material parameters is becoming possible on an increasingly firmer data base. This paper describes recent laser experiments, calculations, and numerical modeling of scintillator response.

Experimental and computational results on exciton/free-carrier ratio, hot/thermalized carrier diffusion, and linear/nonlinear rate constants affecting scintillator proportionality

DOE PAGES

Williams, R. T.; Grim, Joel Q.; Li, Qi; ...

2013-09-26

Models of nonproportional response in scintillators have highlighted the importance of parameters such as branching ratios, carrier thermalization times, diffusion, kinetic order of quenching, associated rate constants, and radius of the electron track. For example, the fraction ηeh of excitations that are free carriers versus excitons was shown by Payne and coworkers to have strong correlation with the shape of electron energy response curves from Compton-coincidence studies. Rate constants for nonlinear quenching are implicit in almost all models of nonproportionality, and some assumption about track radius must invariably be made if one is to relate linear energy deposition dE/dx tomore » volume-based excitation density n (eh/cm 3) in terms of which the rates are defined. Diffusion, affecting time-dependent track radius and thus density of excitations, has been implicated as an important factor in nonlinear light yield. Several groups have recently highlighted diffusion of hot electrons in addition to thermalized carriers and excitons in scintillators. However, experimental determination of many of these parameters in the insulating crystals used as scintillators has seemed difficult. Subpicosecond laser techniques including interband z scan light yield, fluence-dependent decay time, and transient optical absorption are now yielding experimental values for some of the missing rates and ratios needed for modeling scintillator response. First principles calculations and Monte Carlo simulations can fill in additional parameters still unavailable from experiment. As a result, quantitative modeling of scintillator electron energy response from independently determined material parameters is becoming possible on an increasingly firmer data base. This study describes recent laser experiments, calculations, and numerical modeling of scintillator response.« less

The field theory of specific heat

NASA Astrophysics Data System (ADS)

Gusev, Yu. V.

2016-01-01

Finite temperature quantum field theory in the heat kernel method is used to study the heat capacity of condensed matter. The lattice heat is treated à la P. Debye as energy of the elastic (sound) waves. The dimensionless functional of free energy is re-derived with a cut-off parameter and used to obtain the specific heat of crystal lattices. The new dimensionless thermodynamical variable is formed as Planck's inverse temperature divided by the lattice constant. The dimensionless constant, universal for the class of crystal lattices, which determines the low temperature region of molar specific heat, is introduced and tested with the data for diamond lattice crystals. The low temperature asymptotics of specific heat is found to be the fourth power in temperature instead of the cubic power law of the Debye theory. Experimental data for the carbon group elements (silicon, germanium) and other materials decisively confirm the quartic law. The true low temperature regime of specific heat is defined by the surface heat, therefore, it depends on the geometrical characteristics of the body, while the absolute zero temperature limit is geometrically forbidden. The limit on the growth of specific heat at temperatures close to critical points, known as the Dulong-Petit law, appears from the lattice constant cut-off. Its value depends on the lattice type and it is the same for materials with the same crystal lattice. The Dulong-Petit values of compounds are equal to those of elements with the same crystal lattice type, if one mole of solid state matter were taken as the Avogadro number of the composing atoms. Thus, the Neumann-Kopp law is valid only in some special cases.

Irrigation model of bleached Kraft mill wastewater through volcanic soil as a pollutants attenuation process.

PubMed

Navia, R; Inostroza, X; Diez, M C; Lorber, K E

2006-05-01

An irrigation process through volcanic soil columns was evaluated for bleached Kraft mill effluent pollutants retention. The system was designed to remove color and phenolic compounds and a simple kinetic model for determining the global mass transfer coefficient and the adsorption rate constant was used. The results clearly indicate that the global mass transfer coefficient values (K(c)a) and the adsorption rate constants are higher for the irrigation processes onto acidified soil. This means that the pretreatment of washing the volcanic soil with an acid solution has a positive effect on the adsorption rate for both pollutant groups. The enhanced adsorption capacity is partially explained by the activation of the metal oxides present in the soil matrix during the acid washing process. Increasing the flow rate from 1.5 to 2.5 ml/min yielded higher (K(c)a) values and adsorption rate constants for both pollutant groups. For instance, regarding color adsorption onto acidified soil, there is an increment of 43% in the (K(c)a) value for the experiment with a flow rate of 2.5 ml/min. Increasing the porosity of the column from 0.55 to 0.59, yielded a decrease in the (K(c)a) values for color and phenolic compounds adsorption processes. Onto natural soil for example, these decreases reached 21% and 24%, respectively. Therefore, the (K(c)a) value is dependent on both the liquid-phase velocity (external resistance) and the soil fraction in the column (internal resistance); making forced convection and diffusion to be the main transport mechanisms involved in the adsorption process. Analyzing the adsorption rate constants (K(c)a)/m, phenolic compounds and color adsorption rates onto acidified soil of 2.25 x 10(-6) and 2.62 x 10(-6) l/mg min were achieved for experiment 1. These adsorption rates are comparable with other adsorption systems and adsorbent materials.

The effect of concentration- and temperature-dependent dielectric constant on the activity coefficient of NaCl electrolyte solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Valiskó, Mónika; Boda, Dezső, E-mail: boda@almos.vein.hu

2014-06-21

Our implicit-solvent model for the estimation of the excess chemical potential (or, equivalently, the activity coefficient) of electrolytes is based on using a dielectric constant that depends on the thermodynamic state, namely, the temperature and concentration of the electrolyte, ε(c, T). As a consequence, the excess chemical potential is split into two terms corresponding to ion-ion (II) and ion-water (IW) interactions. The II term is obtained from computer simulation using the Primitive Model of electrolytes, while the IW term is estimated from the Born treatment. In our previous work [J. Vincze, M. Valiskó, and D. Boda, “The nonmonotonic concentration dependencemore » of the mean activity coefficient of electrolytes is a result of a balance between solvation and ion-ion correlations,” J. Chem. Phys. 133, 154507 (2010)], we showed that the nonmonotonic concentration dependence of the activity coefficient can be reproduced qualitatively with this II+IW model without using any adjustable parameter. The Pauling radii were used in the calculation of the II term, while experimental solvation free energies were used in the calculation of the IW term. In this work, we analyze the effect of the parameters (dielectric constant, ionic radii, solvation free energy) on the concentration and temperature dependence of the mean activity coefficient of NaCl. We conclude that the II+IW model can explain the experimental behavior using a concentration-dependent dielectric constant and that we do not need the artificial concept of “solvated ionic radius” assumed by earlier studies.« less

Scale-Dependent Rates of Uranyl Surface Complexation Reaction in Sediments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Chongxuan; Shang, Jianying; Kerisit, Sebastien N.

Scale-dependency of uranyl[U(VI)] surface complexation rates was investigated in stirred flow-cell and column systems using a U(VI)-contaminated sediment from the US Department of Energy, Hanford site, WA. The experimental results were used to estimate the apparent rate of U(VI) surface complexation at the grain-scale and in porous media. Numerical simulations using molecular, pore-scale, and continuum models were performed to provide insights into and to estimate the rate constants of U(VI) surface complexation at the different scales. The results showed that the grain-scale rate constant of U(VI) surface complexation was over 3 to 10 orders of magnitude smaller, dependent on themore » temporal scale, than the rate constant calculated using the molecular simulations. The grain-scale rate was faster initially and slower with time, showing the temporal scale-dependency. The largest rate constant at the grain-scale decreased additional 2 orders of magnitude when the rate was scaled to the porous media in the column. The scaling effect from the grain-scale to the porous media became less important for the slower sorption sites. Pore-scale simulations revealed the importance of coupled mass transport and reactions in both intragranular and inter-granular domains, which caused both spatial and temporal dependence of U(VI) surface complexation rates in the sediment. Pore-scale simulations also revealed a new rate-limiting mechanism in the intragranular porous domains that the rate of coupled diffusion and surface complexation reaction was slower than either process alone. The results provided important implications for developing models to scale geochemical/biogeochemical reactions.« less

Potential Energy Surface for Large Barrierless Reaction Systems: Application to the Kinetic Calculations of the Dissociation of Alkanes and the Reverse Recombination Reactions.

PubMed

Yao, Qian; Cao, Xiao-Mei; Zong, Wen-Gang; Sun, Xiao-Hui; Li, Ze-Rong; Li, Xiang-Yuan

2018-05-31

The isodesmic reaction method is applied to calculate the potential energy surface (PES) along the reaction coordinates and the rate constants of the barrierless reactions for unimolecular dissociation reactions of alkanes to form two alkyl radicals and their reverse recombination reactions. The reaction class is divided into 10 subclasses depending upon the type of carbon atoms in the reaction centers. A correction scheme based on isodesmic reaction theory is proposed to correct the PESs at UB3LYP/6-31+G(d,p) level. To validate the accuracy of this scheme, a comparison of the PESs at B3LYP level and the corrected PESs with the PESs at CASPT2/aug-cc-pVTZ level is performed for 13 representative reactions, and it is found that the deviations of the PESs at B3LYP level are up to 35.18 kcal/mol and are reduced to within 2 kcal/mol after correction, indicating that the PESs for barrierless reactions in a subclass can be calculated meaningfully accurately at a low level of ab initio method using our correction scheme. High-pressure limit rate constants and pressure dependent rate constants of these reactions are calculated based on their corrected PESs and the results show the pressure dependence of the rate constants cannot be ignored, especially at high temperatures. Furthermore, the impact of molecular size on the pressure-dependent rate constants of decomposition reactions of alkanes and their reverse reactions has been studied. The present work provides an effective method to generate meaningfully accurate PESs for large molecular system.

Analysis of constant tension-induced rupture of lipid membranes using activation energy.

PubMed

Karal, Mohammad Abu Sayem; Levadnyy, Victor; Yamazaki, Masahito

2016-05-11

The stretching of biomembranes and lipid membranes plays important roles in various physiological and physicochemical phenomena. Here we analyzed the rate constant kp of constant tension-induced rupture of giant unilamellar vesicles (GUVs) as a function of tension σ using their activation energy Ua. To determine the values of kp, we applied constant tension to a GUV membrane using the micropipette aspiration method and observed the rupture of GUVs, and then analyzed these data statistically. First, we investigated the temperature dependence of kp for GUVs of charged lipid membranes composed of negatively charged dioleoylphosphatidylglycerol (DOPG) and electrically neutral dioleoylphosphatidylcholine (DOPC). By analyzing this result, the values of Ua of tension-induced rupture of DOPG/DOPC-GUVs were obtained. Ua decreased with an increase in σ, supporting the classical theory of tension-induced pore formation. The analysis of the relationship between Ua and σ using the theory on the electrostatic interaction effects on the tension-induced rupture of GUVs provided the equation of Ua including electrostatic interaction effects, which well fits the experimental data of the tension dependence of Ua. A constant which does not depend on tension, U0, was also found to contribute significantly to Ua. The Arrhenius equations for kp using the equation of Ua and the parameters determined by the above analysis fit well to the experimental data of the tension dependence of kp for DOPG/DOPC-GUVs as well as for DOPC-GUVs. On the basis of these results, we discussed the possible elementary processes underlying the tension-induced rupture of GUVs of lipid membranes. These results indicate that the Arrhenius equation using the experimentally determined Ua is useful in the analysis of tension-induced rupture of GUVs.

Effect of confinement on anharmonic phonon scattering and thermal conductivity in pristine silicon nanowires

NASA Astrophysics Data System (ADS)

Rashid, Zahid; Zhu, Liyan; Li, Wu

2018-02-01

The effect of confinement on the anharmonic phonon scattering rates and the consequences thereof on the thermal transport properties in ultrathin silicon nanowires with a diameter of 1-4 nm have been characterized using atomistic simulations and the phonon Boltzmann transport equation. The phonon density of states (PDOS) for ultrathin nanowires approaches a constant value in the vicinity of the Γ point and increases with decreasing diameter, which indicates the increasing importance of the low-frequency phonons as heat carriers. The anharmonic phonon scattering becomes dramatically enhanced with decreasing thickness of the nanowires. In the thinnest nanowire, the scattering rates for phonons above 1 THz are one order of magnitude higher than those in the bulk Si. Below 1 THz, the increase in scattering rates is even much more appreciable. Our numerical calculations revealed that the scattering rates for transverse (longitudinal) acoustic modes follow √{ω } (1 /√{ω } ) dependence at the low-frequency limit, whereas those for the degenerate flexural modes asymptotically approach a constant value. In addition, the group velocities of phonons are reduced compared with bulk Si except for low-frequency phonons (<1 -2 THz depending on the thickness of the nanowires). The increased scattering rates combined with reduced group velocities lead to a severely reduced thermal conductivity contribution from the high-frequency phonons. Although the thermal conductivity contributed by those phonons with low frequencies is instead increased mainly due to the increased PDOS, the total thermal conductivity is still reduced compared to that of the bulk. This work reveals an unexplored mechanism to understand the measured ultralow thermal conductivity of silicon nanowires.

Thermodynamic, Spectroscopic, and Computational Studies of f -Element Complexation by N -Hydroxyethyl-diethylenetriamine- N,N ', N ", N"-tetraacetic Acid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grimes, Travis S.; Heathman, Colt R.; Jansone-Popova, Santa

Potentiometric and spectroscopic techniques were combined with DFT calculations to probe the coordination environment and determine thermodynamic features of trivalent f-element complexation by N-hydroxyethyl-diethylenetriamine-N,N',N",N"-tetraacetic acid, HEDTTA. Ligand protonation constants and lanthanide stability constants were determined using potentiometry. Five protonation constants were accessible in I = 2.0 M (H +/Na +)ClO 4. UV–vis spectroscopy was used to determine stability constants for Nd 3+ and Am 3+ complexation with HEDTTA. Luminescence spectroscopy indicates two water molecules in the inner coordination sphere of the Eu/HEDTTA complex, suggesting HEDTTA is heptadentate. Luminescence data was supported by DFT calculations, which demonstrate that substitution of themore » acetate pendant arm by a N-hydroxyethyl group weakens the metal–nitrogen bond. This bond elongation is reflected in HEDTTA’s ability to differentiate trivalent actinides from trivalent lanthanides. The trans-lanthanide Ln/HEDTTA complex stability trend is analogous to Ln/DTPA complexation; however, the loss of one chelate ring resulting from structural substitution weakens the complexation by ~3 orders of magnitude. Successful separation of trivalent americium from trivalent lanthanides was demonstrated when HEDTTA was utilized as aqueous holdback complexant in a liquid–liquid system. Time-dependent extraction studies for HEDTTA were compared to diethylenetriamine-N,N,N',N",N"-pentaacetic acid (DTPA) and N-hydroxyethyl-ethylenediamine-N,N',N'-triacetic acid (HEDTA). The results presented here indicate substantially enhanced phase-transfer kinetic rates for mixtures containing HEDTTA.« less

Thermodynamic, Spectroscopic, and Computational Studies of f -Element Complexation by N -Hydroxyethyl-diethylenetriamine- N,N ', N ", N"-tetraacetic Acid

DOE PAGES

Grimes, Travis S.; Heathman, Colt R.; Jansone-Popova, Santa; ...

2017-01-24

Potentiometric and spectroscopic techniques were combined with DFT calculations to probe the coordination environment and determine thermodynamic features of trivalent f-element complexation by N-hydroxyethyl-diethylenetriamine-N,N',N",N"-tetraacetic acid, HEDTTA. Ligand protonation constants and lanthanide stability constants were determined using potentiometry. Five protonation constants were accessible in I = 2.0 M (H +/Na +)ClO 4. UV–vis spectroscopy was used to determine stability constants for Nd 3+ and Am 3+ complexation with HEDTTA. Luminescence spectroscopy indicates two water molecules in the inner coordination sphere of the Eu/HEDTTA complex, suggesting HEDTTA is heptadentate. Luminescence data was supported by DFT calculations, which demonstrate that substitution of themore » acetate pendant arm by a N-hydroxyethyl group weakens the metal–nitrogen bond. This bond elongation is reflected in HEDTTA’s ability to differentiate trivalent actinides from trivalent lanthanides. The trans-lanthanide Ln/HEDTTA complex stability trend is analogous to Ln/DTPA complexation; however, the loss of one chelate ring resulting from structural substitution weakens the complexation by ~3 orders of magnitude. Successful separation of trivalent americium from trivalent lanthanides was demonstrated when HEDTTA was utilized as aqueous holdback complexant in a liquid–liquid system. Time-dependent extraction studies for HEDTTA were compared to diethylenetriamine-N,N,N',N",N"-pentaacetic acid (DTPA) and N-hydroxyethyl-ethylenediamine-N,N',N'-triacetic acid (HEDTA). The results presented here indicate substantially enhanced phase-transfer kinetic rates for mixtures containing HEDTTA.« less

Rate of reaction of OH with HNO3

NASA Technical Reports Server (NTRS)

Wine, P. H.; Ravishankara, A. R.; Kreutter, N. M.; Shah, R. C.; Nicovich, J. M.; Thompson, R. L.; Wuebbles, D. J.

1981-01-01

Measurements of the kinetics of the reaction of OH with HNO3, and mechanisms of HNO3 removal from the stratosphere, are reported. Bimolecular rate constants were determined at temperatures between 224 and 366 K by monitoring the concentrations of OH radicals produced by HNO3 photolysis and HNO3 according to their resonance fluorescence and 184.9-nm absorption, respectively. The rate constant measured at 298 K is found to be somewhat faster than previously accepted values, with a negative temperature dependence. Calculations of a one-dimensional transport-kinetic atmospheric model on the basis of the new rate constant indicate reductions in O3 depletion due to chlorofluoromethane release and NOx injection, of magnitudes dependent on the nature of the reaction products.

Pressure dependence of the refractive index and dielectric constant in a fluoroperovskite, KMgF3

NASA Astrophysics Data System (ADS)

Uchino, Kenji; Nomura, Shoichiro; Vedam, K.; Newnham, Robert E.; Cross, Leslie E.

1984-06-01

The hydrostatic-pressure dependence of the refractive index and the low-frequency dielectric constant of a perovskite-type single crystal, KMgF3, have been determined at room temperature. The refractive index n for λ=589.3 nm increases monotonously in proportion to pressure p with a slope of ∂n∂p=2.46×10-4kbar-1. On the other hand, the dielectric constant at 10 kHz decreases with increasing pressure, from which the electric-displacement-related electrostrictive coefficient Qh (=Q11+2Q12) is calculated as 0.24 m4 C-2. These data are compared with the ∂n∂p values and the Qh coefficients of various alkali fluorides and perovskite oxides.

Time and voltage dependences of nanoscale dielectric constant modulation on indium tin oxide films

NASA Astrophysics Data System (ADS)

Li, Liang; Hao, Haoyue; Zhao, Hua

2017-01-01

The modulation of indium tin oxide (ITO) films through surface charge accumulation plays an important role in many different applications. In order to elaborately study the modulation, we measured the dielectric constant of the modulated layer through examining the excitation of surface plasmon polaritons. Charges were pumped on the surfaces of ITO films through applying high voltage in appropriate directions. Experiments unveiled that the dielectric constant of the modulated layer had large variation along with the nanoscale charge accumulation. Corresponding numerical results were worked out through combining Drude model and Mayadas-Shatzkes model. Based on the above results, we deduced the time and voltage dependences of accumulated charge density, which revealed a long-time charge accumulation process.

A nonmonotonic dependence of standard rate constant on reorganization energy for heterogeneous electron transfer processes on electrode surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xu Weilin; Li Songtao; Zhou Xiaochun

2006-05-07

In the present work a nonmonotonic dependence of standard rate constant (k{sup 0}) on reorganization energy ({lambda}) was discovered qualitatively from electron transfer (Marcus-Hush-Levich) theory for heterogeneous electron transfer processes on electrode surface. It was found that the nonmonotonic dependence of k{sup 0} on {lambda} is another result, besides the disappearance of the famous Marcus inverted region, coming from the continuum of electronic states in electrode: with the increase of {lambda}, the states for both Process I and Process II ET processes all vary from nonadiabatic to adiabatic state continuously, and the {lambda} dependence of k{sup 0} for Process Imore » is monotonic thoroughly, while for Process II on electrode surface the {lambda} dependence of k{sup 0} could show a nonmonotonicity.« less

Retro-Nasal Aroma Release Is Correlated with Variations in the In-Mouth Air Cavity Volume after Empty Deglutition

PubMed Central

Mishellany-Dutour, Anne; Woda, Alain; Labouré, Hélène; Bourdiol, Pierre; Lachaze, Pauline; Guichard, Elisabeth; Feron, Gilles

2012-01-01

We hypothesized that interindividual differences in motor activities during chewing and/or swallowing were determining factors for the transfer of volatile aroma from the in-mouth air cavity (IMAC) toward the olfactory mucosa. In our first experiment, we looked for changes in IMAC volume after saliva deglutition in 12 healthy subjects. The mean IMAC volume was measured after empty deglutition using an acoustic pharyngometer device. Based on the time course of the IMAC volume after swallowing, we discerned two groups of subjects. The first group displayed a small, constant IMAC volume (2.26 mL ±0.62) that corresponded to a high tongue position. The second group displayed a progressive increase in IMAC (from 6.82 mL ±2.37 to 22.82 mL ±3.04) that corresponded to a progressive lowering of the tongue to its resting position. In our second experiment, we investigated the relationship between IMAC volume changes after deglutition and the level of aroma release at the nostril. For this purpose, the release of menthone was measured at the nostril level in 25 subjects who consumed similar amounts of a mint tablet. The subjects were separated into two groups corresponding to two levels of menthone release: high (H) and low (L). The mean volume of IMAC was measured during and after empty deglutition. Group H displayed a small, constant amplitude of IMAC volume change after deglutition, while Group L displayed a progressive increase in IMAC. It is likely that Group H continuously released the aroma through the veloglossal isthmus as the mint was consumed, while Group L trapped the aroma in the oral cavity and then released it into the nasal cavity upon swallowing. These results show that the in vivo aroma release profile in humans depends closely on the different motor patterns at work during empty deglutition. PMID:22815986

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gadzhaliev, M. M.; Daunov, M. I.; Musaev, A. M., E-mail: akhmed-musaev@yandex.ru

The pressure dependence of permittivity χ of direct gap ZnO, CdTe, InSb, InAs, CdSnAs{sub 2}, and CdGeAs{sub 2} semiconductors in the hydrostatic pressure range from zero to 1 GPa is determined from the results of quantitative analysis of the pressure dependences of resistivity ρ(P) and Hall constant R{sub H}(P). It is found that the dielectric constant decreases upon an increase in pressure so that coefficient (dχ/d{sub P})/χ increases with (dE{sub g}/dP)/E{sub g}.

Correction to “Comment on ‘Equilibrium Constants and Rate Constants for Adsorbates: 2D Ideal Gas, 2D Ideal Lattice Gas, and Ideal Hindered Translator Models’”

DOE PAGES

Savara, Aditya

2017-06-28

There was an error in the original Comment. The entropy term arising from 1/N! should be free from dimensional dependence, but also negative. In the original Comment, the nN A arising from 1/N! was inadvertently moved into the dimensional dependent term of Eqs. 2 and 3. To avoid confusion and to keep the same numbering as before, the equations should be as follows.

Characterization of OSL dosimeters for use in dose assessment in Computed Tomography procedures.

PubMed

Giansante, Louise; Santos, Josilene C; Umisedo, Nancy K; Terini, Ricardo A; Costa, Paulo R

2018-03-01

This study describes the characterization of an Al 2 O 3 :C OSLD (Landauer's Luxel™ tape) for dose evaluation in Computed Tomography. The irradiations were conducted using both a constant potential X-ray equipment and a 64-slice clinical CT scanner, and the readouts were performed using a Risø TL/OSL reader. The following aspects were studied: batch homogeneity, energy response, linearity of dose response, reproducibility, reusability, and effect of uncertainties with the normalization of OSL signals per their response to beta radiation. A group of 330 dosimeters from the 452 irradiated with the same dose presented OSL signals within the interval of 4.7% from the average. The dosimeters presented energy-dependent response in good agreement with results found in the literature. The air kerma response of the OSL signal showed a linear trend for both the constant potential X-ray device and the clinical CT scanner, with differences in their slopes of approximately 10%. Reproducibility, reusability, and effect of beta normalization were analyzed by separating 72 dosimeters in 3 groups. The results obtained in this study together with those of previous works indicate that this type of dosimeter is adequate for dose evaluation in CT clinical applications. Copyright © 2018 Associazione Italiana di Fisica Medica. Published by Elsevier Ltd. All rights reserved.

A Semi-Empirical Two Step Carbon Corrosion Reaction Model in PEM Fuel Cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Young, Alan; Colbow, Vesna; Harvey, David

2013-01-01

The cathode CL of a polymer electrolyte membrane fuel cell (PEMFC) was exposed to high potentials, 1.0 to 1.4 V versus a reversible hydrogen electrode (RHE), that are typically encountered during start up/shut down operation. While both platinum dissolution and carbon corrosion occurred, the carbon corrosion effects were isolated and modeled. The presented model separates the carbon corrosion process into two reaction steps; (1) oxidation of the carbon surface to carbon-oxygen groups, and (2) further corrosion of the oxidized surface to carbon dioxide/monoxide. To oxidize and corrode the cathode catalyst carbon support, the CL was subjected to an accelerated stressmore » test cycled the potential from 0.6 VRHE to an upper potential limit (UPL) ranging from 0.9 to 1.4 VRHE at varying dwell times. The reaction rate constants and specific capacitances of carbon and platinum were fitted by evaluating the double layer capacitance (Cdl) trends. Carbon surface oxidation increased the Cdl due to increased specific capacitance for carbon surfaces with carbon-oxygen groups, while the second corrosion reaction decreased the Cdl due to loss of the overall carbon surface area. The first oxidation step differed between carbon types, while both reaction rate constants were found to have a dependency on UPL, temperature, and gas relative humidity.« less

Ultrasound Induced Fluorescence of Nanoscale Liposome Contrast Agents

PubMed Central

Zhang, Qimei; Morgan, Stephen P.; O’Shea, Paul; Mather, Melissa L.

2016-01-01

A new imaging contrast agent is reported that provides an increased fluorescent signal upon application of ultrasound (US). Liposomes containing lipids labelled with pyrene were optically excited and the excimer fluorescence emission intensity was detected in the absence and presence of an ultrasound field using an acousto-fluorescence setup. The acousto-fluorescence dynamics of liposomes containing lipids with pyrene labelled on the fatty acid tail group (PyPC) and the head group (PyPE) were compared. An increase in excimer emission intensity following exposure to US was observed for both cases studied. The increased intensity and time constants were found to be different for the PyPC and PyPE systems, and dependent on the applied US pressure and exposure time. The greatest change in fluorescence intensity (130%) and smallest rise time constant (0.33 s) are achieved through the use of PyPC labelled liposomes. The mechanism underlying the observed increase of the excimer emission intensity in PyPC labelled liposomes is proposed to arise from the “wagging” of acyl chains which involves fast response and requires lower US pressure. This is accompanied by increased lipid lateral diffusivity at higher ultrasound pressures, a mechanism that is also active in the PyPE labelled liposomes. PMID:27467748

Constants for mercury binding by organic matter isolates from the Florida Everglades

USGS Publications Warehouse

Benoit, J.M.; Mason, R.P.; Gilmour, C.C.; Aiken, G.R.

2001-01-01

Dissolved organic matter (DOM) has been implicated as an important complexing agent for Hg that can affect its mobility and bioavailability in aquatic ecosystems. However, binding constants for natural Hg-DOM complexes are not well known. We employed a competitive ligand approach to estimate conditional stability constants for Hg complexes with DOM isolates collected from Florida Everglades surface waters. The isolates examined were the hydrophobic fraction of DOM from a eutrophic, sulfidic site (F1-HPoA) and the hydrophilic fraction from an oligotrophic, low-sulfide site (2BS-HPiA). Our experimental determinations utilized overall octanol-water partitioning coefficients (Dow) for 203Hg at 0.01 M chloride and across pH and DOM concentration gradients. Use of this radioisotope allowed rapid determinations of Hg concentrations in both water and octanol phases without problems of matrix interference. Conditional stability constants (1 = 0.06, 23??C) were log K??? = 11.8 for F1-HPoA and log K' = 10.6 for 2BS-HPiA. These are similar to previously published stability constants for Hg binding to low-molecular-weight thiols. Further, F1-HPoA showed a pH-dependent decline in Dow that was consistent with models of Hg complexation with thiol groups as the dominant Hg binding sites in DOM. These experiments demonstrate that the DOM isolates are stronger ligands for Hg than chloride ion or ethylenediamine-tetraacetic acid. Speciation calculations indicate that at the DOM concentrations frequently measured in Everglades, 20 to 40 ??M, significant complexation of Hg by DOM would be expected in aerobic (sulfide-free) surface waters. Copyright ?? 2001 Elsevier Science Ltd.

Study of the hydrolysis and ionization constants of Schiff base from pyridoxal 5'-phosphate and n-hexylamine in partially aqueous solvents. An application to phosphorylase b.

PubMed Central

Donoso, J; Muñoz, F; García Del Vado, A; Echevarría, G; García Blanco, F

1986-01-01

Formation and hydrolysis rate constants as well as equilibrium constants of the Schiff base derived from pyridoxal 5'-phosphate and n-hexylamine were determined between pH 3.5 and 7.5 in ethanol/water mixtures (3:17, v/v, and 49:1, v/v). The results indicate that solvent polarity scarcely alters the values of these constants but that they are dependent on the pH. Spectrophotometric titration of this Schiff base was also carried out. We found that a pKa value of 6.1, attributed in high-polarity media to protonation of the pyridine nitrogen atom, is independent of solvent polarity, whereas the pKa of the monoprotonated form of the imine falls from 12.5 in ethanol/water (3:17) to 11.3 in ethanol/water (49:1). Fitting of the experimental results for the hydrolysis to a theoretical model indicates the existence of a group with a pKa value of 6.1 that is crucial in the variation of kinetic constant of hydrolysis with pH. Studies of the reactivity of the coenzyme (pyridoxal 5'-phosphate) of glycogen phosphorylase b with hydroxylamine show that this reaction only occurs when the pH value of solution is below 6.5 and the hydrolysis of imine bond has started. We propose that the decrease in activity of phosphorylase b when the pH value is less than 6.2 must be caused by the cleavage of enzyme-coenzyme binding and that this may be related with protonation of the pyridine nitrogen atom of pyridoxal 5'-phosphate. PMID:3099764

Third-order Douglas-Kroll Relativistic Coupled-Cluster Theory through Connected Single, Double, Triple, and Quadruple Substitutions: Applications to Diatomic and Triatomic Hydrides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hirata, So; Yanai, Takeshi; De Jong, Wibe A.

Coupled-cluster methods including through and up to the connected single, double, triple, and quadruple substitutions (CCSD, CCSDT, and CCSDTQ) have been automatically derived and implemented for sequential and parallel executions for use in conjunction with a one-component third-order Douglas-Kroll (DK3) approximation for relativistic corrections. A combination of the converging electron-correlation methods, the accurate relativistic reference wave functions, and the use of systematic basis sets tailored to the relativistic approximation has been shown to predict the experimental singlet-triplet separations within 0.02 eV (0.5 kcal/mol) for five triatomic hydrides (CH2, NH2+, SiH2, PH2+, and AsH2+), the experimental bond lengths within 0.002 angstroms,more » rotational constants within 0.02 cm-1, vibration-rotation constants within 0.01 cm-1, centrifugal distortion constants within 2 %, harmonic vibration frequencies within 9 cm-1 (0.4 %), anharmonic vibrational constants within 2 cm-1, and dissociation energies within 0.03 eV (0.8 kcal/mol) for twenty diatomic hydrides (BH, CH, NH, OH, FH, AlH, SiH, PH, SH, ClH, GaH, GeH, AsH, SeH, BrH, InH, SnH, SbH, TeH, and IH) containing main-group elements across the second through fifth periods of the periodic table. In these calculations, spin-orbit effects on dissociation energies, which were assumed to be additive, were estimated from the measured spin-orbit coupling constants of atoms and diatomic molecules, and an electronic energy in the complete-basis-set, complete-electron-correlation limit has been extrapolated by the formula which was in turn based on the exponential-Gaussian extrapolation formula of the basis set dependence.« less

Investigation of Saltwater Intrusion and Recirculation of Seawater for Henry Constant Dispersion and Velocity-Dependent Dispersion Problems and Field-Scale Problem

NASA Astrophysics Data System (ADS)

Motz, L. H.; Kalakan, C.

2013-12-01

Three problems regarding saltwater intrusion, namely the Henry constant dispersion and velocity-dependent dispersion problems and a larger, field-scale velocity-dependent dispersion problem, have been investigated to determine quantitatively how saltwater intrusion and the recirculation of seawater at a coastal boundary are related to the freshwater inflow and the density-driven buoyancy flux. Based on dimensional analysis, saltwater intrusion and the recirculation of seawater are dependent functions of the independent ratio of freshwater advective flux relative to the density-driven vertical buoyancy flux, defined as az (or a for an isotropic aquifer), and the aspect ratio of horizontal and vertical dimensions of the cross-section. For the Henry constant dispersion problem, in which the aquifer is isotropic, saltwater intrusion and recirculation are related to an additional independent dimensionless parameter that is the ratio of the constant dispersion coefficient treated as a scalar quantity, the porosity, and the freshwater advective flux, defined as b. For the Henry velocity-dependent dispersion problem, the ratio b is zero, and saltwater intrusion and recirculation are related to an additional independent dimensionless parameter that is the ratio of the vertical and horizontal dispersivities, or rα = αz/αx. For an anisotropic aquifer, saltwater intrusion and recirculation are also dependent on the ratio of vertical and horizontal hydraulic conductivities, or rK = Kz/Kx. For the field-scale velocity-dependent dispersion problem, saltwater intrusion and recirculation are dependent on the same independent ratios as the Henry velocity-dependent dispersion problem. In the two-dimensional cross-section for all three problems, freshwater inflow occurs at an upgradient boundary, and recirculated seawater outflow occurs at a downgradient coastal boundary. The upgradient boundary is a specified-flux boundary with zero freshwater concentration, and the downgradient boundary is a specified-head boundary with a specified concentration equal to seawater. Equivalent freshwater heads are specified at the downstream boundary to account for density differences between freshwater and saltwater at the downstream boundary. The three problems were solved using the numerical groundwater flow and transport code SEAWAT for two conditions, i.e., first for the uncoupled condition in which the fluid density is constant and thus the flow and transport equations are uncoupled in a constant-density flowfield, and then for the coupled condition in which the fluid density is a function of the total dissolved solids concentration and thus the flow and transport equations are coupled in a variable-density flowfield. A wide range of results for the landward extent of saltwater intrusion and the amount of recirculation of seawater at the coastal boundary was obtained by varying the independent dimensionless ratio az (or a in problem one) in all three problems. The dimensionless dispersion ratio b was also varied in problem one, and the dispersivity ratio rα and the hydraulic conductivity ratio rK were also varied in problems two and three.

Theory of single-molecule controlled rotation experiments, predictions, tests, and comparison with stalling experiments in F1-ATPase.

PubMed

Volkán-Kacsó, Sándor; Marcus, Rudolph A

2016-10-25

A recently proposed chemomechanical group transfer theory of rotary biomolecular motors is applied to treat single-molecule controlled rotation experiments. In these experiments, single-molecule fluorescence is used to measure the binding and release rate constants of nucleotides by monitoring the occupancy of binding sites. It is shown how missed events of nucleotide binding and release in these experiments can be corrected using theory, with F 1 -ATP synthase as an example. The missed events are significant when the reverse rate is very fast. Using the theory the actual rate constants in the controlled rotation experiments and the corrections are predicted from independent data, including other single-molecule rotation and ensemble biochemical experiments. The effective torsional elastic constant is found to depend on the binding/releasing nucleotide, and it is smaller for ADP than for ATP. There is a good agreement, with no adjustable parameters, between the theoretical and experimental results of controlled rotation experiments and stalling experiments, for the range of angles where the data overlap. This agreement is perhaps all the more surprising because it occurs even though the binding and release of fluorescent nucleotides is monitored at single-site occupancy concentrations, whereas the stalling and free rotation experiments have multiple-site occupancy.

[COMPLICATIONS OF PREGNANCY, RESULTING FROM ASSISTED REPRODUCTIVE TECHNOLOGY].

PubMed

Aleksanyan, A

2017-01-01

When pregnancy occurs as a result of assisted reproductive technologies (ART), there are more chances of developing complications and adverse outcomes for the mother and fetus compared to spontaneous pregnancies. Taking into account the noted features, the purpose of our study was to determine the nature of the complications of induced pregnancy and their frequency, depending on the causes of infertility. Under our supervision were 86 women with induced single-pregnancy. Two clinical groups were formed depending on the causes of infertility: group I was represented by 53 observations, in which infertility of endocrine genesis took place; Group II included 33 women with tubal peritoneal infertility. Pregnancy, resulting from ART, should be attributed to the group at high risk of complications of pregnancy. Among the causes of female infertility, the tubal peritoneal factor is the least dangerous in terms of the complicated course of the gestational process, and the endocrine factors that can cause a two-fold increase in the frequency of the threat of abortion and pre-eclampsia are more dangerous. In turn, the cause of endocrine infertility are various factors that need to be determined when predicting the course of induced pregnancy. A special feature of maintaining this category of pregnant women is the constant observation and correction of dyshormonal disorders, which not only cause anovulation, but can also negatively affect the course of pregnancy.

Assessment of rate of drug release from oil vehicle using a rotating dialysis cell.

PubMed

Larsen, D H; Fredholt, K; Larsen, C

2000-09-01

The rate constants for transfer of model compounds (naproxen and lidocaine) from oily vehicle (Viscoleo) to aqueous buffer phases were determined by use of the rotating dialysis cell. Release studies were done for the partly ionized compounds at several pH values. A correlation between the overall first-order rate constant related to attainment of equilibrium, k(obs), and the pH-dependent distribution coefficient, D, determined between oil vehicle and aqueous buffer was established according to the equation: logk(obs)=-0.71 logD-0.22 (k(obs) in h(-1)). Based on this correlation it was suggested that the rate constant of a weak electrolyte at a specified D value could be considered equal to the k(obs) value for a non-electrolyte possessing a partition coefficient, P(app), the magnitude of which was equal to D. Specific rate constants k(ow) and k(wo) were calculated from the overall rate constant and the pH-dependent distribution coefficient. The rate constant representing the transport from oily vehicle to aqueous phase, k(ow), was found to be significantly influenced by the magnitude of the partition coefficient P(app) according to: logk(ow)=-0.71 logP(app)-log(P(app)+1)-0.22 (k(ow) in h(-1)).

The effect of the magnetic nanoparticle's size dependence of the relaxation time constant on the specific loss power of magnetic nanoparticle hyperthermia

NASA Astrophysics Data System (ADS)

Harabech, Mariem; Leliaert, Jonathan; Coene, Annelies; Crevecoeur, Guillaume; Van Roost, Dirk; Dupré, Luc

2017-03-01

Magnetic nanoparticle hyperthermia is a cancer treatment in which magnetic nanoparticles (MNPs) are subjected to an alternating magnetic field to induce heat in the tumor. The generated heat of MNPs is characterized by the specific loss power (SLP) due to relaxation phenomena of the MNP. Up to now, several models have been proposed to predict the SLP, one of which is the Linear Response Theory. One parameter in this model is the relaxation time constant. In this contribution, we employ a macrospin model based on the Landau-Lifshitz-Gilbert equation to investigate the relation between the Gilbert damping parameter and the relaxation time constant. This relaxation time has a pre-factor τ0 which is often taken as a fixed value ranging between 10-8 and 10-12 s. However, in reality it has small size dependence. Here, the influence of this size dependence on the calculation of the SLP is demonstrated, consequently improving the accuracy of this estimate.

The Coulomb based magneto-electric coupling in multiferroic tunnel junctions and granular multiferroics

NASA Astrophysics Data System (ADS)

Udalov, O. G.; Beloborodov, I. S.

2018-05-01

We study magneto-electric effect in two systems: i) multiferroic tunnel junction (MFTJ) - magnetic tunnel junction with ferroelectric barrier and ii) granular multiferroic (GMF) in which ferromagnetic (FM) metallic grains embedded into ferroelectric matrix. We show that the Coulomb interaction influences the magnetic state of the system in several ways: i) through the spin-dependent part of the Coulomb interaction; ii) due to the Coulomb blockade effect suppressing electron hopping and therefore reducing magnetic coupling; and iii) through image forces and polarization screening that modify the barrier for electrons in MFTJ and GMF. We show that in the absence of spin-orbit or strain-mediated coupling magneto-electric effect appears in GMF and MFTJ. The Coulomb interaction depends on the dielectric properties of the system. For GMF it depends on the dielectric constant of FE matrix and for MFTJ on the dielectric constant of the FE barrier. Applying external electric field one can tune the dielectric constant and the Coulomb interaction. Thus, one can control magnetic state with electric field.

Doppler-resolved kinetics of saturation recovery

DOE PAGES

Forthomme, Damien; Hause, Michael L.; Yu, Hua -Gen; ...

2015-04-08

Frequency modulated laser transient absorption has been used to monitor the ground state rotational energy transfer rates of CN radicals in a double-resonance, depletion recovery experiment. When a pulsed laser is used to burn a hole in the equilibrium ground state population of one rotational state without velocity selection, the population recovery rate is found to depend strongly on the Doppler detuning of a narrow-band probe laser. Similar effects should be apparent for any relaxation rate process that competes effectively with velocity randomization. Alternative methods of extracting thermal rate constants in the presence of these non-thermal conditions are evaluated. Totalmore » recovery rate constants, analogous to total removal rate constants in an experiment preparing a single initial rotational level, are in good agreement with quantum scattering calculations, but are slower than previously reported experiments and show qualitatively different rotational state dependence between Ar and He collision partners. As a result, quasi-classical trajectory studies confirm that the differing rotational state dependence is primarily a kinematic effect.« less

Pressure Dependence of the Boson Peak of Glassy Glycerol

DOE PAGES

Ahart, Muhtar; Aihaiti, Dilare; Hemley, Russell J.; ...

2017-05-31

The pressure dependence of the Boson peak (BP) of glycerol, including its behavior across the liquid-glass transition, has been studied under pressure using Raman scattering. A significant increase of the BP frequency was observed with pressure up to 11 GPa at room temperature. The pressure dependence of BP frequency ν BP is proportional to (1+P/P 0) 1/3, where P and P 0 are the pressure and a constant, respectively, the spectra are consistent with a soft potential model. The characteristic length of medium range order is close in size to a cyclic trimer of glycerol molecules, which is predicted asmore » the medium range order of a BP vibration using molecular dynamics simulations. The pressure dependence of a characteristic length of medium range order is nearly constant. The pressure induced structural changes in glycerol can be understood in terms of the shrinkage of voids with cyclic trimers remaining up to at least 11 GPa. Lastly, the pressure dependence of intermolecular O-H stretching mode indicates that the intermolecular hydrogen bond distance gradually decreases below the glass transition pressure of ~5 GPa, while it becomes nearly constant in the glassy state indicating the disappearance of the free volume in the dense glass.« less

New constraints on time-dependent variations of fundamental constants using Planck data

NASA Astrophysics Data System (ADS)

Hart, Luke; Chluba, Jens

2018-02-01

Observations of the cosmic microwave background (CMB) today allow us to answer detailed questions about the properties of our Universe, targeting both standard and non-standard physics. In this paper, we study the effects of varying fundamental constants (i.e. the fine-structure constant, αEM, and electron rest mass, me) around last scattering using the recombination codes COSMOREC and RECFAST++. We approach the problem in a pedagogical manner, illustrating the importance of various effects on the free electron fraction, Thomson visibility function and CMB power spectra, highlighting various degeneracies. We demonstrate that the simpler RECFAST++ treatment (based on a three-level atom approach) can be used to accurately represent the full computation of COSMOREC. We also include explicit time-dependent variations using a phenomenological power-law description. We reproduce previous Planck 2013 results in our analysis. Assuming constant variations relative to the standard values, we find the improved constraints αEM/αEM, 0 = 0.9993 ± 0.0025 (CMB only) and me/me, 0 = 1.0039 ± 0.0074 (including BAO) using Planck 2015 data. For a redshift-dependent variation, αEM(z) = αEM(z0) [(1 + z)/1100]p with αEM(z0) ≡ αEM, 0 at z0 = 1100, we obtain p = 0.0008 ± 0.0025. Allowing simultaneous variations of αEM(z0) and p yields αEM(z0)/αEM, 0 = 0.9998 ± 0.0036 and p = 0.0006 ± 0.0036. We also discuss combined limits on αEM and me. Our analysis shows that existing data are not only sensitive to the value of the fundamental constants around recombination but also its first time derivative. This suggests that a wider class of varying fundamental constant models can be probed using the CMB.

Concentration dependence of biotransformation in fish liver S9: Optimizing substrate concentrations to estimate hepatic clearance for bioaccumulation assessment.

PubMed

Lo, Justin C; Allard, Gayatri N; Otton, S Victoria; Campbell, David A; Gobas, Frank A P C

2015-12-01

In vitro bioassays to estimate biotransformation rate constants of contaminants in fish are currently being investigated to improve bioaccumulation assessments of hydrophobic contaminants. The present study investigates the relationship between chemical substrate concentration and in vitro biotransformation rate of 4 environmental contaminants (9-methylanthracene, pyrene, chrysene, and benzo[a]pyrene) in rainbow trout (Oncorhynchus mykiss) liver S9 fractions and methods to determine maximum first-order biotransformation rate constants. Substrate depletion experiments using a series of initial substrate concentrations showed that in vitro biotransformation rates exhibit strong concentration dependence, consistent with a Michaelis-Menten kinetic model. The results indicate that depletion rate constants measured at initial substrate concentrations of 1 μM (a current convention) could underestimate the in vitro biotransformation potential and may cause bioconcentration factors to be overestimated if in vitro biotransformation rates are used to assess bioconcentration factors in fish. Depletion rate constants measured using thin-film sorbent dosing experiments were not statistically different from the maximum depletion rate constants derived using a series of solvent delivery-based depletion experiments for 3 of the 4 test chemicals. Multiple solvent delivery-based depletion experiments at a range of initial concentrations are recommended for determining the concentration dependence of in vitro biotransformation rates in fish liver fractions, whereas a single sorbent phase dosing experiment may be able to provide reasonable approximations of maximum depletion rates of very hydrophobic substances. © 2015 SETAC.

Trees, bialgebras and intrinsic numerical algorithms

NASA Technical Reports Server (NTRS)

Crouch, Peter; Grossman, Robert; Larson, Richard

1990-01-01

Preliminary work about intrinsic numerical integrators evolving on groups is described. Fix a finite dimensional Lie group G; let g denote its Lie algebra, and let Y(sub 1),...,Y(sub N) denote a basis of g. A class of numerical algorithms is presented that approximate solutions to differential equations evolving on G of the form: dot-x(t) = F(x(t)), x(0) = p is an element of G. The algorithms depend upon constants c(sub i) and c(sub ij), for i = 1,...,k and j is less than i. The algorithms have the property that if the algorithm starts on the group, then it remains on the group. In addition, they also have the property that if G is the abelian group R(N), then the algorithm becomes the classical Runge-Kutta algorithm. The Cayley algebra generated by labeled, ordered trees is used to generate the equations that the coefficients c(sub i) and c(sub ij) must satisfy in order for the algorithm to yield an rth order numerical integrator and to analyze the resulting algorithms.

Influence of the pressure dependent coefficient of friction on deep drawing springback predictions

NASA Astrophysics Data System (ADS)

Gil, Imanol; Galdos, Lander; Mendiguren, Joseba; Mugarra, Endika; Sáenz de Argandoña, Eneko

2016-10-01

This research studies the effect of considering an advanced variable friction coefficient on the springback prediction of stamping processes. Traditional constant coefficient of friction considerations are being replaced by more advanced friction coefficient definitions. The aim of this work is to show the influence of defining a pressure dependent friction coefficient on numerical springback predictions of a DX54D mild steel, a HSLA380 and a DP780 high strength steel. The pressure dependent friction model of each material was fitted to the experimental data obtained by Strip Drawing tests. Then, these friction models were implemented in a numerical simulation of a drawing process of an industrial automotive part. The results showed important differences between defining a pressure dependent friction coefficient or a constant friction coefficient.

Is the cosmological constant screened in Liouville gravity with matter?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Inami, Takeo; Koyama, Yoji; Nakayama, Yu

In this study, there has been a proposal that infrared quantum effects of massless interacting field theories in de Sitter space may provide time-dependent screening of the cosmological constant. As a concrete model of the proposal, we study the three loop corrections to the energy–momentum tensor of massless λΦ 4 theory in the background of classical Liouville gravity in D = 2 dimensional de Sitter space. We find that the cosmological constant is screened, in sharp contrast to the massless λΦ 4 theory in D = 4 dimensions due to the sign difference between the cosmological constant of the Liouvillemore » gravity and that of the Einstein gravity. To argue for the robustness of our prediction, we introduce the concept of time-dependent infrared counter-terms and examine if they recover the de Sitter invariance in the λΦ 4 theory in comparison with the Sine–Gordon model, where it was possible.« less

Monte Carlo modeling the phase diagram of magnets with the Dzyaloshinskii - Moriya interaction

NASA Astrophysics Data System (ADS)

Belemuk, A. M.; Stishov, S. M.

2017-11-01

We use classical Monte Carlo calculations to model the high-pressure behavior of the phase transition in the helical magnets. We vary values of the exchange interaction constant J and the Dzyaloshinskii-Moriya interaction constant D, which is equivalent to changing spin-spin distances, as occurs in real systems under pressure. The system under study is self-similar at D / J = constant , and its properties are defined by the single variable J / T , where T is temperature. The existence of the first order phase transition critically depends on the ratio D / J . A variation of J strongly affects the phase transition temperature and width of the fluctuation region (the ;hump;) as follows from the system self-similarity. The high-pressure behavior of the spin system depends on the evolution of the interaction constants J and D on compression. Our calculations are relevant to the high pressure phase diagrams of helical magnets MnSi and Cu2OSeO3.

Quantification of the dielectric constant of single non-spherical nanoparticles from polarization forces: eccentricity effects.

PubMed

Gomila, G; Esteban-Ferrer, D; Fumagalli, L

2013-12-20

We analyze by means of finite-element numerical calculations the polarization force between a sharp conducting tip and a non-spherical uncharged dielectric nanoparticle with the objective of quantifying its dielectric constant from electrostatic force microscopy (EFM) measurements. We show that for an oblate spheroid nanoparticle of given height the strength of the polarization force acting on the tip depends linearly on the eccentricity, e, of the nanoparticle in the small eccentricity and low dielectric constant regimes (1 < e < 2 and 1 < ε(r) < 10), while for higher eccentricities (e > 2) the dependence is sub-linear and finally becomes independent of e for very large eccentricities (e > 30). These results imply that a precise account of the nanoparticle shape is required to quantify EFM data and obtain the dielectric constants of non-spherical dielectric nanoparticles. Experimental results obtained on polystyrene, silicon dioxide and aluminum oxide nanoparticles and on single viruses are used to illustrate the main findings.

Influence of humic acid addition on the degradation of pharmaceuticals by biofilms in effluent wastewater.

PubMed

Tang, Kai; Escola Casas, Monica; Ooi, Gordon T H; Kaarsholm, Kamilla M S; Bester, Kai; Andersen, Henrik R

2017-05-01

The degradation of organic micropollutants in wastewater treatment is suspected to depend on co-degradation i.e. be dependent on concentrations of substrate. This complicates predicting and modelling their fate. The effect of humic acid, as a model for complex organic substrate, was investigated in relation to the biodegradation of pharmaceuticals by suspended biofilm carriers adapted to polishing effluent water from a tertiary sewage treatment plant. Twelve out of 22 investigated pharmaceuticals were significantly biodegradable. The biodegradation rate constants of ten of those compounds were increasing with increased humic acid concentrations. At the highest humic acid concentration (30mgC/L), the biodegradation rate constants were four times higher than the biodegradation rate constants without added humic acid. This shows that the presence of complex substrate stimulates degradation via a co-metabolism-like mechanism and competitive inhibition does not occur. Increases of rate constant per mgC/L are tentatively calculated. Copyright © 2017 Elsevier GmbH. All rights reserved.

Volatility dependence of Henry's law constants of condensable organics: Application to estimate depositional loss of secondary organic aerosols

NASA Astrophysics Data System (ADS)

Hodzic, A.; Aumont, B.; Knote, C.; Lee-Taylor, J.; Madronich, S.; Tyndall, G.

2014-07-01

The water solubility of oxidation intermediates of volatile organic compounds that can condense to form secondary organic aerosol (SOA) is largely unconstrained in current chemistry-climate models. We apply the Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere to calculate Henry's law constants for these intermediate species. Results show a strong negative correlation between Henry's law constants and saturation vapor pressures. Details depend on precursor species, extent of photochemical processing, and NOx levels. Henry's law constants as a function of volatility are made available over a wide range of vapor pressures for use in 3-D models. In an application using the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) over the U.S. in summer, we find that dry (and wet) deposition of condensable organic vapors leads to major reductions in SOA, decreasing surface concentrations by ~50% (10%) for biogenic and ~40% (6%) for short chain anthropogenic precursors under the considered volatility conditions.

Is the cosmological constant screened in Liouville gravity with matter?

DOE PAGES

Inami, Takeo; Koyama, Yoji; Nakayama, Yu; ...

2015-05-19

In this study, there has been a proposal that infrared quantum effects of massless interacting field theories in de Sitter space may provide time-dependent screening of the cosmological constant. As a concrete model of the proposal, we study the three loop corrections to the energy–momentum tensor of massless λΦ 4 theory in the background of classical Liouville gravity in D = 2 dimensional de Sitter space. We find that the cosmological constant is screened, in sharp contrast to the massless λΦ 4 theory in D = 4 dimensions due to the sign difference between the cosmological constant of the Liouvillemore » gravity and that of the Einstein gravity. To argue for the robustness of our prediction, we introduce the concept of time-dependent infrared counter-terms and examine if they recover the de Sitter invariance in the λΦ 4 theory in comparison with the Sine–Gordon model, where it was possible.« less

Electronic polarizability of light crude oil from optical and dielectric studies

NASA Astrophysics Data System (ADS)

George, A. K.; Singh, R. N.

2017-07-01

In the present paper we report the temperature dependence of density, refractive indices and dielectric constant of three samples of crude oils. The API gravity number estimated from the temperature dependent density studies revealed that the three samples fall in the category of light oil. The measured data of refractive index and the density are used to evaluate the polarizability of these fluids. Molar refractive index and the molar volume are evaluated through Lorentz-Lorenz equation. The function of the refractive index, FRI , divided by the mass density ρ, is a constant approximately equal to one-third and is invariant with temperature for all the samples. The measured values of the dielectric constant decrease linearly with increasing temperature for all the samples. The dielectric constant estimated from the refractive index measurements using Lorentz-Lorentz equation agrees well with the measured values. The results are promising since all the three measured properties complement each other and offer a simple and reliable method for estimating crude oil properties, in the absence of sufficient data.

Menadione metabolism to thiodione in hepatoblastoma by scanning electrochemical microscopy

PubMed Central

Mauzeroll, Janine; Bard, Allen J.; Owhadian, Omeed; Monks, Terrence J.

2004-01-01

The cytotoxicity of menadione on hepatocytes was studied by using the substrate generation/tip collection mode of scanning electrochemical microscopy by exposing the cells to menadione and detecting the menadione-S-glutathione conjugate (thiodione) that is formed during the cellular detoxication process and is exported from the cell by an ATP-dependent pump. This efflux was electrochemically detected and allowed scanning electrochemical microscopy monitoring and imaging of single cells and groups of highly confluent live cells. Based on a constant flux model, ≈6 × 106 molecules of thiodione per cell per second are exported from monolayer cultures of Hep G2 cells. PMID:15601769

A Successful Attempt to Obtain the Linear Dependence Between One-Photon and Two-Photon Spectral Properties and Hammett Parameters of Various Aromatic Substituents in New π-Extended Asymmetric Organic Chromophores.

PubMed

Hu, Nvdan; Gong, Yulong; Wang, Xinchao; Lu, Yao; Peng, Guangyue; Yang, Long; Zhang, Shengtao; Luo, Ziping; Li, Hongru; Gao, Fang

2015-11-01

A series of new asymmetric chromophores containing aromatic substituents and possessing the excellent π-extension in space were prepared through multi-steps routes. One-photon and two-photon spectral properties of these new chromophores could be tuned by these substituents finely and simultaneously. The linear correlation of the wave numbers of the one-photon absorption and emission maxima to Hammett parameters of these substituents was presented. Near infrared two-photon absorption emission integrated areas of the target chromophores were correlated linearly to Hammett constants of these substituted groups.

Conversion of ultrashort laser pulses to wavelengths above 3 mm in tapered germanate fibres

NASA Astrophysics Data System (ADS)

Anashkina, E. A.; Andrianov, A. V.; Kim, A. V.

2015-05-01

Tapered germanate fibres are proposed for effective adiabatic conversion of Raman soliton pulses to the mid-IR region. A theoretical analysis demonstrates that, in fibres with anomalous group velocity dispersion decreasing along their length, wavelengths of up to 3.5 μm can be reached, which are unattainable in fibres with a constant core diameter at the same parameters of a 2-μm input signal. The analysis relies on a one-way wave equation that takes into account the combined effect of dispersion, Kerr and Raman nonlinearities, nonlinear dispersion and optical losses and the frequency dependence of the effective fundamental transverse mode size.

Waves in a plane graphene - dielectric waveguide structure

NASA Astrophysics Data System (ADS)

Evseev, Dmitry A.; Eliseeva, Svetlana V.; Sementsov, Dmitry I.

2017-10-01

The features of the guided TE modes propagation have been investigated on the basis of computer simulations in a planar structure consisting of a set of alternating layers of dielectric and graphene. Within the framework of the effective medium approximation, the dispersion relations have been received for symmetric and antisymmetric waveguide modes, determined by the frequency range of their existence. The wave field distribution by structure, frequency dependences of the constants of propagation and transverse components of the wave vectors, as well as group and phase velocities of waveguide modes have been obtained, the effect of the graphene part in a structure on the waveguide mode behavior has been shown.

Linear response of mutans streptococci to increasing frequency of xylitol chewing gum use: a randomized controlled trial [ISRCTN43479664].

PubMed

Ly, Kiet A; Milgrom, Peter; Roberts, Marilyn C; Yamaguchi, David K; Rothen, Marilynn; Mueller, Greg

2006-03-24

Xylitol is a naturally occurring sugar substitute that has been shown to reduce the level of mutans streptococci in plaque and saliva and to reduce tooth decay. It has been suggested that the degree of reduction is dependent on both the amount and the frequency of xylitol consumption. For xylitol to be successfully and cost-effectively used in public health prevention strategies dosing and frequency guidelines should be established. This study determined the reduction in mutans streptococci levels in plaque and unstimulated saliva to increasing frequency of xylitol gum use at a fixed total daily dose of 10.32 g over five weeks. Participants (n = 132) were randomized to either active groups (10.32 g xylitol/day) or a placebo control (9.828 g sorbitol and 0.7 g maltitol/day). All groups chewed 12 pieces of gum per day. The control group chewed 4 times/day and active groups chewed xylitol gum at a frequency of 2 times/day, 3 times/day, or 4 times/day. The 12 gum pieces were evenly divided into the frequency assigned to each group. Plaque and unstimulated saliva samples were taken at baseline and five-weeks and were cultured on modified Mitis Salivarius agar for mutans streptococci enumeration. There were no significant differences in mutans streptococci level among the groups at baseline. At five-weeks, mutans streptococci levels in plaque and unstimulated saliva showed a linear reduction with increasing frequency of xylitol chewing gum use at the constant daily dose. Although the difference observed for the group that chewed xylitol 2 times/day was consistent with the linear model, the difference was not significant. There was a linear reduction in mutans streptococci levels in plaque and saliva with increasing frequency of xylitol gum use at a constant daily dose. Reduction at a consumption frequency of 2 times per day was small and consistent with the linear-response line but was not statistically significant.

Narrative means to manage responsibility in life narratives across adolescence.

PubMed

De Silveira, Cybèle; Habermas, Tilmann

2011-01-01

Adolescence is a passage from dependence to adult responsibility. Alongside identity development, social-cognitive development, and the ability to construct a life story, adolescents become increasingly aware of both their potential responsibility in an expanded sphere of life and of complex, contextual influences on their lives. This was partially tested in a cross-sectional study, both in terms of linguistic means and content expressed in life narratives. Indicators were defined for narrative agency, grading of responsibility, serendipity, and turning points, and tested for age differences in relative frequencies in 102 life narratives from age groups of 8, 12, 16, and 20 years, balanced for gender. Narrative grading of responsibility, serendipity, and turning points increased throughout adolescence. The relative frequency of narrative agency, in contrast, remained constant across age groups. Results are interpreted in the context of adolescent development of narrative identity.

Frequency dependence of sensitivities in second-order RC active filters

NASA Astrophysics Data System (ADS)

Kunieda, T.; Hiramatsu, Y.; Fukui, A.

1980-02-01

This paper presents that gain and phase sensitivities to some element in biquadratic filters approximately constitute a circle on the complex sensitivity plane, provided that the quality factor Q of the circuit is appreciably larger than unity. Moreover, the group delay sensitivity is represented by the imaginary part of a cardioid. Using these results, bounds of maximum values of gain, phase, and group delay sensitivities are obtained. Further, it is proved that the maximum values of these sensitivities can be simultaneously minimized by minimizing the absolute value of the transfer function sensitivity at the center frequency provided that w(0)-sensitivities are constant and do not contain design parameters. Next, a statistical variability measure for the optimal-filter design is proposed. Finally, the relation between some variability measures proposed to the present time is made clear.

Functional group quantification of polymer nanomembranes with soft x-rays

NASA Astrophysics Data System (ADS)

Sunday, Daniel F.; Chan, Edwin P.; Orski, Sara V.; Nieuwendaal, Ryan C.; Stafford, Christopher M.

2018-03-01

Polyamide nanomembranes are at the heart of water desalination, a process which plays a critical role in clean water production. Improving their efficiency requires a better understanding of the relationship between chemistry, network structure, and performance but few techniques afford compositional information in ultrathin films (<100 nm). Here, we leverage resonant soft x-ray reflectivity, a measurement that is sensitive to the specific chemical bonds in organic materials, to quantify the functional group concentration in these polyamides. We first employ reference materials to establish quantitative relationships between changes in the optical constants and functional group density, and then use the results to evaluate the functional group concentrations of polyamide nanomembranes. We demonstrate that the difference in the amide carbonyl and carboxylic acid group concentrations can be used to calculate the crosslink density, which is shown to vary significantly across three different polyamide chemistries. A clear relationship is established between the functional group density and the permselectivity (α ), indicating that more densely crosslinked materials result in a higher α of the nanomembranes. Finally, measurements on a polyamide/poly(acrylic acid) bilayer demonstrate the ability of this approach to quantify depth-dependent functional group concentrations in thin films.

Extracting Diffusion Constants from Echo-Time-Dependent PFG NMR Data Using Relaxation-Time Information

NASA Astrophysics Data System (ADS)

Vandusschoten, D.; Dejager, P. A.; Vanas, H.

Heterogeneous (bio)systems are often characterized by several water-containing compartments that differ in relaxation time values and diffusion constants. Because of the relatively small differences among these diffusion constants, nonoptimal measuring conditions easily lead to the conclusion that a single diffusion constant suffices to describe the water mobility in a heterogeneous (bio)system. This paper demonstrates that the combination of a T2 measurement and diffusion measurements at various echo times (TE), based on the PFG MSE sequence, enables the accurate determination of diffusion constants which are less than a factor of 2 apart. This new method gives errors of the diffusion constant below 10% when two fractions are present, while the standard approach of a biexponential fit to the diffusion data in identical circumstances gives larger (>25%) errors. On application of this approach to water in apple parenchyma tissue, the diffusion constant of water in the vacuole of the cells ( D = 1.7 × 10 -9 m 2/s) can be distinguished from that of the cytoplasm ( D = 1.0 × 10 -9 m 2/s). Also, for mung bean seedlings, the cell size determined by PFG MSE measurements increased from 65 to 100 μm when the echo time increased from 150 to 900 ms, demonstrating that the interpretation of PFG SE data used to investigate cell sizes is strongly dependent on the T2 values of the fractions within the sample. Because relaxation times are used to discriminate the diffusion constants, we propose to name this approach diffusion analysis by relaxation- time- separated (DARTS) PFG NMR.

On the radiative and thermodynamic properties of the cosmic radiations using COBE FIRAS instrument data: I. Cosmic microwave background radiation

NASA Astrophysics Data System (ADS)

Fisenko, Anatoliy I.; Lemberg, Vladimir

2014-07-01

Using the explicit form of the functions to describe the monopole and dipole spectra of the Cosmic Microwave Background (CMB) radiation, the exact expressions for the temperature dependences of the radiative and thermodynamic functions, such as the total radiation power per unit area, total energy density, number density of photons, Helmholtz free energy density, entropy density, heat capacity at constant volume, and pressure in the finite range of frequencies v 1≤ v≤ v 2 are obtained. Since the dependence of temperature upon the redshift z is known, the obtained expressions can be simply presented in z representation. Utilizing experimental data for the monopole and dipole spectra measured by the COBE FIRAS instrument in the 60-600 GHz frequency interval at the temperature T=2.72548 K, the values of the radiative and thermodynamic functions, as well as the radiation density constant a and the Stefan-Boltzmann constant σ are calculated. In the case of the dipole spectrum, the constants a and σ, and the radiative and thermodynamic properties of the CMB radiation are obtained using the mean amplitude T amp=3.358 mK. It is shown that the Doppler shift leads to a renormalization of the radiation density constant a, the Stefan-Boltzmann constant σ, and the corresponding constants for the thermodynamic functions. The expressions for new astrophysical parameters, such as the entropy density/Boltzmann constant, and number density of CMB photons are obtained. The radiative and thermodynamic properties of the Cosmic Microwave Background radiation for the monopole and dipole spectra at redshift z≈1089 are calculated.

Search for time modulations in the decay constant of 40K and 226Ra at the underground Gran Sasso Laboratory

NASA Astrophysics Data System (ADS)

Bellotti, E.; Broggini, C.; Di Carlo, G.; Laubenstein, M.; Menegazzo, R.

2018-05-01

Time modulations at per mil level have been reported to take place in the decay constant of several nuclei with period of one year (most cases) but also of about one month or one day. On the other hand, experiments with similar or better sensitivity have been unable to detect any modulation. In this letter we give the results of the activity study of two different sources: 40K and 226Ra. The two gamma spectrometry experiments have been performed underground at the Gran Sasso Laboratory, this way suppressing the time dependent cosmic ray background. Briefly, our measurements reached the sensitivity of 3.4 and 3.5 parts over 106 for 40K and 226Ra, respectively (1 sigma) and they do not show any statistically significant evidence of time dependence in the decay constant. We also give the results of the activity measurement at the time of the two strong X-class solar flares which took place in September 2017. Our data do not show any unexpected time dependence in the decay rate of 40K in correspondence with the two flares. To the best of our knowledge, these are the most precise and accurate results on the stability of the decay constant as function of time.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ahart, Muhtar; Aihaiti, Dilare; Hemley, Russell J.

The pressure dependence of the Boson peak (BP) of glycerol, including its behavior across the liquid-glass transition, has been studied under pressure using Raman scattering. A significant increase of the BP frequency was observed with pressure up to 11 GPa at room temperature. The pressure dependence of BP frequency ν BP is proportional to (1+P/P 0) 1/3, where P and P 0 are the pressure and a constant, respectively, the spectra are consistent with a soft potential model. The characteristic length of medium range order is close in size to a cyclic trimer of glycerol molecules, which is predicted asmore » the medium range order of a BP vibration using molecular dynamics simulations. The pressure dependence of a characteristic length of medium range order is nearly constant. The pressure induced structural changes in glycerol can be understood in terms of the shrinkage of voids with cyclic trimers remaining up to at least 11 GPa. Lastly, the pressure dependence of intermolecular O-H stretching mode indicates that the intermolecular hydrogen bond distance gradually decreases below the glass transition pressure of ~5 GPa, while it becomes nearly constant in the glassy state indicating the disappearance of the free volume in the dense glass.« less

The n-propyl 3-azido-2,3-dideoxy-β-D-arabino-hexopyranoside: Syntheses, crystal structure, physical properties and stability constants of their complexes with Cu(II), Ni(II) and VO(II)

NASA Astrophysics Data System (ADS)

Barabaś, Anna; Madura, Izabela D.; Marek, Paulina H.; Dąbrowska, Aleksandra M.

2017-11-01

The structure, conformation and configuration of the n-propyl 3-azido-2,3-dideoxy-β-D-arabino-hexopyranoside (BAra-nPr) were determined by 1H NMR, 13C NMR, and IR spectroscopy, as well as by optical rotation. The crystal structure was confirmed by single-crystal X-ray diffraction studies at room temperature. The compound crystallizes in P21 space group symmetry of the monoclinic system. The molecule has a 4C1 chair conformation with azide group in the equatorial position both in a solution as well as in the crystal. The spatial arrangement of azide group is compared to other previously determined azidosugars. The hydrogen bonds between the hydroxyl group of sugar molecules lead to a ribbon structure observed also for the ethyl homolog. The packing of ribbons is dependent on the alkyl substituent length and with the elongation changes from pseudohexagonal to lamellar. Acidity constants for the n-propyl 3-azido-2,3-dideoxy-β-D-arabino-hexopyranoside (BAra-nPr) in an aqueous solution were evaluated by the spectrophotometric and potentiometric titrations methods. Title compound exhibit blue absorption with the maximum wavelengths in the range of 266 nm and 306 nm. Based on these measurements we showed equilibria existing in a particular solution and a distribution of species which have formed during the titration. We also investigated interactions between Cu(II), Ni(II) and VO(II) and title compound (as ligand L) during complexometric titration. On these bases we identified that in [CuII-BAra-nPr]2+ the ratio of the ligand L to metal ion M(II) was 3:1, while in [NiII-BAra-nPr]2+ and [VOII-BAra-nPr]2+ complexes 2:1 ratios were found. The cumulative stability constants (as log β) occurring in an aqueous solution for the complexes of BAra-nPr with Cu(II), Ni(II) and VO(IV) were 14.57; 11.71 and 4.20, respectively.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wiedemeier, Heribert, E-mail: wiedeh@rpi.edu

The observed linear (Na-, K-halides) and near-linear (Mg-, Sr-, Zn-, Cd-, and Hg-chalcogenides) dependences of Schottky constants on reciprocal interatomic distances yield the relation logK{sub S}=((s{sub s}1/T)+i{sub s})1/d{sub (A−B)}+(s{sub i}1/T)+i{sub i}, where K{sub S} is the product of metal and non-metal thermal equilibrium vacancy concentrations, and s{sub s}, i{sub s}, s{sub i} and i{sub i} are the group specific slope and intercept values obtained from an extended analysis of the above log K{sub S} versus 1/d{sub (A−B)} data. The previously reported linear dependences of log K{sub S} on the Born–Haber lattice energies [1] are the basis for combining the earliermore » results [1] with the Born–Mayer lattice energy equation to yield a new thermodynamic relationship, namely logK{sub S}=−(2.303nRT){sup −1}(c{sub (B−M)}/d{sub (A−B)}−I{sub e}), where c{sub (B−M)} is the product of the constants of the Born–Mayer equation and I{sub e} is the metal ionization energy of the above compounds. These results establish a correlation between point defect concentrations and basic thermodynamic, coulombic, and structural solid state properties for selected I–VII and II–VI semiconductor materials. - Graphical abstract: Display Omitted.« less

Does precision decrease with set size?

PubMed Central

Mazyar, Helga; van den Berg, Ronald; Ma, Wei Ji

2012-01-01

The brain encodes visual information with limited precision. Contradictory evidence exists as to whether the precision with which an item is encoded depends on the number of stimuli in a display (set size). Some studies have found evidence that precision decreases with set size, but others have reported constant precision. These groups of studies differed in two ways. The studies that reported a decrease used displays with heterogeneous stimuli and tasks with a short-term memory component, while the ones that reported constancy used homogeneous stimuli and tasks that did not require short-term memory. To disentangle the effects of heterogeneity and short-memory involvement, we conducted two main experiments. In Experiment 1, stimuli were heterogeneous, and we compared a condition in which target identity was revealed before the stimulus display with one in which it was revealed afterward. In Experiment 2, target identity was fixed, and we compared heterogeneous and homogeneous distractor conditions. In both experiments, we compared an optimal-observer model in which precision is constant with set size with one in which it depends on set size. We found that precision decreases with set size when the distractors are heterogeneous, regardless of whether short-term memory is involved, but not when it is homogeneous. This suggests that heterogeneity, not short-term memory, is the critical factor. In addition, we found that precision exhibits variability across items and trials, which may partly be caused by attentional fluctuations. PMID:22685337

Nonempirical range-separated hybrid functionals for solids and molecules

DOE PAGES

Skone, Jonathan H.; Govoni, Marco; Galli, Giulia

2016-06-03

Dielectric-dependent hybrid (DDH) functionals were recently shown to yield accurate energy gaps and dielectric constants for a wide variety of solids, at a computational cost considerably less than that of GW calculations. The fraction of exact exchange included in the definition of DDH functionals depends (self-consistently) on the dielectric constant of the material. Here we introduce a range-separated (RS) version of DDH functionals where short and long-range components are matched using system dependent, non-empirical parameters. We show that RS DDHs yield accurate electronic properties of inorganic and organic solids, including energy gaps and absolute ionization potentials. Moreover, we show thatmore » these functionals may be generalized to finite systems.« less

Dilemma of dilemmas: how collective and individual perspectives can clarify the size dilemma in voluntary linear public goods dilemmas.

PubMed

Shank, Daniel B; Kashima, Yoshihisa; Saber, Saam; Gale, Thomas; Kirley, Michael

2015-01-01

Empirical findings on public goods dilemmas indicate an unresolved dilemma: that increasing size-the number of people in the dilemma-sometimes increases, decreases, or does not influence cooperation. We clarify this dilemma by first classifying public goods dilemma properties that specify individual outcomes as individual properties (e.g., Marginal Per Capita Return) and group outcomes as group properties (e.g., public good multiplier), mathematically showing how only one set of properties can remain constant as the dilemma size increases. Underpinning decision-making regarding individual and group properties, we propose that individuals are motivated by both individual and group preferences based on a theory of collective rationality. We use Van Lange's integrated model of social value orientations to operationalize these preferences as an amalgamation of outcomes for self, outcomes for others, and equality of outcomes. Based on this model, we then predict how the public good's benefit and size, combined with controlling individual versus group properties, produce different levels of cooperation in public goods dilemmas. A two (low vs. high benefit) by three (2-person baseline vs. 5-person holding constant individual properties vs. 5-person holding constant group properties) factorial experiment (group n = 99; participant n = 390) confirms our hypotheses. The results indicate that when holding constant group properties, size decreases cooperation. Yet when holding constant individual properties, size increases cooperation when benefit is low and does not affect cooperation when benefit is high. Using agent-based simulations of individual and group preferences vis-à-vis the integrative model, we fit a weighted simulation model to the empirical data. This fitted model is sufficient to reproduce the empirical results, but only when both individual (self-interest) and group (other-interest and equality) preference are included. Our research contributes to understanding how people's motivations and behaviors within public goods dilemmas interact with the properties of the dilemma to lead to collective outcomes.

Dilemma of Dilemmas: How Collective and Individual Perspectives Can Clarify the Size Dilemma in Voluntary Linear Public Goods Dilemmas

PubMed Central

Shank, Daniel B.; Kashima, Yoshihisa; Saber, Saam; Gale, Thomas; Kirley, Michael

2015-01-01

Empirical findings on public goods dilemmas indicate an unresolved dilemma: that increasing size—the number of people in the dilemma—sometimes increases, decreases, or does not influence cooperation. We clarify this dilemma by first classifying public goods dilemma properties that specify individual outcomes as individual properties (e.g., Marginal Per Capita Return) and group outcomes as group properties (e.g., public good multiplier), mathematically showing how only one set of properties can remain constant as the dilemma size increases. Underpinning decision-making regarding individual and group properties, we propose that individuals are motivated by both individual and group preferences based on a theory of collective rationality. We use Van Lange's integrated model of social value orientations to operationalize these preferences as an amalgamation of outcomes for self, outcomes for others, and equality of outcomes. Based on this model, we then predict how the public good's benefit and size, combined with controlling individual versus group properties, produce different levels of cooperation in public goods dilemmas. A two (low vs. high benefit) by three (2-person baseline vs. 5-person holding constant individual properties vs. 5-person holding constant group properties) factorial experiment (group n = 99; participant n = 390) confirms our hypotheses. The results indicate that when holding constant group properties, size decreases cooperation. Yet when holding constant individual properties, size increases cooperation when benefit is low and does not affect cooperation when benefit is high. Using agent-based simulations of individual and group preferences vis-à-vis the integrative model, we fit a weighted simulation model to the empirical data. This fitted model is sufficient to reproduce the empirical results, but only when both individual (self-interest) and group (other-interest and equality) preference are included. Our research contributes to understanding how people's motivations and behaviors within public goods dilemmas interact with the properties of the dilemma to lead to collective outcomes. PMID:25799355

A surface complexation model of YREE sorption on Ulva lactuca in 0.05-5.0 M NaCl solutions

NASA Astrophysics Data System (ADS)

Zoll, Alison M.; Schijf, Johan

2012-11-01

We present distribution coefficients, log iKS, for the sorption of yttrium and the rare earth elements (YREEs) on BCR-279, a dehydrated tissue homogenate of a marine macroalga, Ulva lactuca, resembling materials featured in chemical engineering studies aimed at designing renewable biosorbents. Sorption experiments were conducted in NaCl solutions of different ionic strength (0.05, 0.5, and 5.0 M) at T = 25 °C over the pH range 2.7-8.5. Distribution coefficients based on separation of the dissolved and particulate phase by conventional filtration (<0.22 μm) were corrected for the effect of colloid-bound YREEs (>3 kDa) using an existing pH-dependent model. Colloid-corrected values were renormalized to free-cation concentrations by accounting for YREE hydrolysis and chloride complexation. At each ionic strength, the pH dependence of the renormalized values is accurately described with a non-electrostatic surface complexation model (SCM) that incorporates YREE binding to three monoprotic functional groups, previously characterized by alkalimetric titration, as well as binding of YREE-hydroxide complexes (MOH2+) to the least acidic one (pKa ∼ 9.5). In non-linear regressions of the distribution coefficients as a function of pH, each pKa was fixed at its reported value, while stability constants of the four YREE surface complexes were used as adjustable parameters. Data for a single fresh U. lactuca specimen in 0.5 M NaCl show generally the same pH-dependent behavior but a lower degree of sorption and were excluded from the regressions. Good linear free-energy relations (LFERs) between stability constants of the YREE-acetate and YREE-hydroxide solution complex and surface complexes with the first and third functional group, respectively, support their prior tentative identifications as carboxyl and phenol. A similar confirmation for the second group is precluded by insufficient knowledge of the stability of YREE-phosphate complexes and a perceived lack of YREE binding in 0.05 M NaCl; this issue awaits further study. The results indicate that SCMs can be successfully applied to sorbents as daunting as marine organic matter. Despite remnant challenges, for instance resolving the contributions of individual groups to the aggregate sorption signal, our approach helps formalize seaweed’s avowed promise as an ideal biomonitor or biofilter of metal pollution in environments ranging from freshwaters to brines by uncovering what chemical mechanisms underlie its pronounced affinity for YREEs and other surface-reactive elements.

Time-dependent local potential in a Tomonaga-Luttinger liquid

NASA Astrophysics Data System (ADS)

Kamar, Naushad Ahmad; Giamarchi, Thierry

2017-12-01

We study the energy deposition in a one-dimensional interacting quantum system with a pointlike potential modulated in amplitude. The pointlike potential at position x =0 has a constant part and a small oscillation in time with a frequency ω . We use bosonization, renormalization group, and linear response theory to calculate the corresponding energy deposition. It exhibits a power law behavior as a function of the frequency that reflects the Tomonaga-Luttinger liquid (TLL) nature of the system. Depending on the interactions in the system, characterized by the TLL parameter K of the system, a crossover between weak and strong coupling for the backscattering due to the potential is possible. We compute the frequency scale ω*, at which such crossover exists. We find that the energy deposition due to the backscattering shows different exponents for K >1 and K <1 . We discuss possible experimental consequences, in the context of cold atomic gases, of our theoretical results.

Imidazole C-2 Hydrogen/Deuterium Exchange Reaction at Histidine for Probing Protein Structure and Function with MALDI Mass Spectrometry

PubMed Central

Hayashi, Naoka; Kuyama, Hiroki; Nakajima, Chihiro; Kawahara, Kazuki; Miyagi, Masaru; Nishimura, Osamu; Matsuo, Hisayuki; Nakazawa, Takashi

2015-01-01

We present a mass spectrometric method for analyzing protein structure and function, based on the imidazole C-2 or histidine Cε1 hydrogen/deuterium (H/D) exchange reaction, which is intrinsically second order with respect to the concentrations of the imidazolium cation and OD− in D2O. The second-order rate constant (k2) of this reaction was calculated from the pH-dependency of the pseudo-first-order rate constant (kφ) obtained from the change of average mass ΔMr (0 ≤ ΔMr < 1) of a peptide fragment containing a defined histidine residue at incubation time (t) such that kφ = − [ln(1−ΔMr)]/t. We preferred using k2 rather than kφ because k2max (maximal value of k2) was empirically related to pKa as illustrated with a Brønsted plot: logk2max=-0.7pKa+α (α is an arbitrary constant), so that we could analyze the effect of structure on the H/D-exchange rate in terms of log(k2max/k2) representing the deviation of k2 from k2max. In the catalytic site of bovine ribonuclease A, His12 showed much larger change in log(k2max/k2) compared with His119 upon binding with cytidine 3′-monophosphate, as anticipated from the X-ray structures and the possible change in solvent accessibility. However, there is a need of considering the hydrogen bonds of the imidazole group with non-dissociable groups to interpret an extremely slow H/D exchange rate of His48 in partially solvent-exposed situation. PMID:24606199

Cost associated with stroke: outpatient rehabilitative services and medication.

PubMed

Godwin, Kyler M; Wasserman, Joan; Ostwald, Sharon K

2011-10-01

This study aimed to capture direct costs of outpatient rehabilitative stroke care and medications for a 1-year period after discharge from inpatient rehabilitation. Outpatient rehabilitative services and medication costs for 1 year, during the time period of 2001 to 2005, were calculated for 54 first-time stroke survivors. Costs for services were based on Medicare reimbursement rates. Medicaid reimbursement rates and average wholesale price were used to estimate medication costs. Of the 54 stroke survivors, 40 (74.1%) were categorized as independent, 12 (22.2%) had modified dependence, and 2 (3.7%) were dependent at the time of discharge from inpatient rehabilitation. Average cost for outpatient stroke rehabilitation services and medications the first year post inpatient rehabilitation discharge was $17,081. The corresponding average yearly cost of medication was $5,392, while the average cost of yearly rehabilitation service utilization was $11,689. Cost attributed to medication remained relatively constant throughout the groups. Outpatient rehabilitation service utilization constituted a large portion of cost within each group: 69.7% (dependent), 72.5% (modified dependence), and 66.7% (independent). Stroke survivors continue to incur significant costs associated with their stroke for the first 12 months following discharge from an inpatient rehabilitation setting. Changing public policies affect the cost and availability of care. This study provides a snapshot of outpatient medication and therapy costs prior to the enactment of major changes in federal legislation and serves as a baseline for future studies.

Coupling time constants of striated and copper-plated coated conductors and the potential of striation to reduce shielding-current-induced fields in pancake coils

NASA Astrophysics Data System (ADS)

Amemiya, Naoyuki; Tominaga, Naoki; Toyomoto, Ryuki; Nishimoto, Takuma; Sogabe, Yusuke; Yamano, Satoshi; Sakamoto, Hisaki

2018-07-01

The shielding-current-induced field is a serious concern for the applications of coated conductors to magnets. The striation of the coated conductor is one of the countermeasures, but it is effective only after the decay of the coupling current, which is characterised with the coupling time constant. In a non-twisted striated coated conductor, the coupling time constant is determined primarily by its length and the transverse resistance between superconductor filaments, because the coupling current could flow along its entire length. We measured and numerically calculated the frequency dependences of magnetisation losses in striated and copper-plated coated conductors with various lengths and their stacks at 77 K and determined their coupling time constants. Stacked conductors simulate the turns of a conductor wound into a pancake coil. Coupling time constants are proportional to the square of the conductor length. Stacking striated coated conductors increases the coupling time constants because the coupling currents in stacked conductors are coupled to one another magnetically to increase the mutual inductances for the coupling current paths. We carried out the numerical electromagnetic field analysis of conductors wound into pancake coils and determined their coupling time constants. They can be explained by the length dependence and mutual coupling effect observed in stacked straight conductors. Even in pancake coils with practical numbers of turns, i.e. conductor lengths, the striation is effective to reduce the shielding-current-induced fields for some dc applications.

Modelling of the acid-base properties of natural and synthetic adsorbent materials used for heavy metal removal from aqueous solutions.

PubMed

Pagnanelli, Francesca; Vegliò, Francesco; Toro, Luigi

2004-02-01

In this paper a comparison about kinetic behaviour, acid-base properties and copper removal capacities was carried out between two different adsorbent materials used for heavy metal removal from aqueous solutions: an aminodiacetic chelating resin as commercial product (Lewatit TP207) and a lyophilised bacterial biomass of Sphaerotilus natans. The acid-base properties of a S. natans cell suspension were well described by simplified mechanistic models without electrostatic corrections considering two kinds of weakly acidic active sites. In particular the introduction of two-peak distribution function for the proton affinity constants allows a better representation of the experimental data reproducing the site heterogeneity. A priori knowledge about resin functional groups (aminodiacetic groups) is the base for preliminary simulations of titration curve assuming a Donnan gel structure for the resin phase considered as a concentrated aqueous solution of aminodiacetic acid (ADA). Departures from experimental and simulated data can be interpreted by considering the heterogeneity of the functional groups and the effect of ionic concentration in the resin phase. Two-site continuous model describes adequately the experimental data. Moreover the values of apparent protonation constants (as adjustable parameters found by non-linear regression) are very near to the apparent constants evaluated by a Donnan model assuming the intrinsic constants in resin phase equal to the equilibrium constants in aqueous solution of ADA and considering the amphoteric nature of active sites for the evaluation of counter-ion concentration in the resin phase. Copper removal outlined the strong affinity of the active groups of the resin for this ion in solution compared to the S. natans biomass according to the complexation constants between aminodiacetic and mono-carboxylic groups and copper ions.

A survey on anticancer effects of artemisinin, iron, miconazole, and butyric acid on 5637 (bladder cancer) and 4T1 (Breast cancer) cell lines.

PubMed

Shahbazfar, Amir Ali; Zare, Payman; Ranjbaran, Mehrdad; Tayefi-Nasrabadi, Hossein; Fakhri, Omid; Farshi, Yashar; Shadi, Sahar; Khoshkerdar, Afsaneh

2014-01-01

Anticancer properties of artemisinin and its derivatives have been shown in many experiments. Addition of butyric acid, miconazole, and iron to this traditional drug has been done in order to enhance its anticancer potency. Cell lines 5637 and 4T1, were cultivated and classified into 13 groups of three each. Different doses of artemisinin with constant doses of iron, miconazole and butyric acid, were added to the cultures. At the end of exposure pathological and enzymatic studies were performed. In four groups treated with different doses of artemisinin and iron, dose-dependent changes were observed. These changes included apoptosis and necrosis with dominance of apoptosis. The supernatant lactate dehydrogenase (LDH) level was increased in a dose-dependent manner, but there was no significant increase in the cell fraction of malonyldialdehyde (MDA) or LDH. In four other groups, which received miconazole, butyric acid and iron in addition to different doses of artemisinin, necrosis was more prominent than apoptosis, and the MDA level did not show any significant change, but LDH was increased. The groups treated with miconazole showed identical changes, with less severity compared to combination therapy groups. In butyric acid-treated groups, the only detectable changes were, mild cell swelling, few apoptosis, and rare necrosis. A combination therapy with artemisinin can be more effective against cancer cells than monotherapy with that. Butyric acid was not effective on cancer cells. Miconazole deviated the nature of cell death from apoptosis to necrosis and it must be used under caution.

Determination of magneto-optical constant of Fe films with weak measurements

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qiu, Xiaodong; Hu, Dejiao; Du, Jinglei

2014-09-29

In this letter, a detecting method for the magneto-optical constant is presented by using weak measurements. The photonic spin Hall effect (PSHE), which manifests itself as spin-dependent splitting, is introduced to characterize the magneto-optical constant, and a propagation model to describe the quantitative relation between the magneto-optical constant and the PSHE is established. According to the amplified shift of the PSHE detected by weak measurements, we determinate the magneto-optical constant of the Fe film sample. The Kerr rotation is measured via the standard polarimetry method to verify the rationality and feasibility of our method. These findings may provide possible applicationsmore » in magnetic physics research.« less

Synthesizing Dynamic Programming Algorithms from Linear Temporal Logic Formulae

NASA Technical Reports Server (NTRS)

Rosu, Grigore; Havelund, Klaus

2001-01-01

The problem of testing a linear temporal logic (LTL) formula on a finite execution trace of events, generated by an executing program, occurs naturally in runtime analysis of software. We present an algorithm which takes an LTL formula and generates an efficient dynamic programming algorithm. The generated algorithm tests whether the LTL formula is satisfied by a finite trace of events given as input. The generated algorithm runs in linear time, its constant depending on the size of the LTL formula. The memory needed is constant, also depending on the size of the formula.

Classification of light sources and their interaction with active and passive environments

NASA Astrophysics Data System (ADS)

El-Dardiry, Ramy G. S.; Faez, Sanli; Lagendijk, Ad

2011-03-01

Emission from a molecular light source depends on its optical and chemical environment. This dependence is different for various sources. We present a general classification in terms of constant-amplitude and constant-power sources. Using this classification, we have described the response to both changes in the local density of states and stimulated emission. The unforeseen consequences of this classification are illustrated for photonic studies by random laser experiments and are in good agreement with our correspondingly developed theory. Our results require a revision of studies on sources in complex media.

Temperature Dependence of Errors in Parameters Derived from Van't Hoff Studies.

ERIC Educational Resources Information Center

Dec, Steven F.; Gill, Stanley J.

1985-01-01

The method of Clarke and Glew is broadly applicable to studies of the temperature dependence of equilibrium constant measurements. The method is described and examples of its use in comparing calorimetric results and temperature dependent gas solubility studies are provided. (JN)

Pressure-limited sustained inflation vs. gradual tidal inflations for resuscitation in preterm lambs.

PubMed

Tingay, David G; Polglase, Graeme R; Bhatia, Risha; Berry, Clare A; Kopotic, Robert J; Kopotic, Clinton P; Song, Yong; Szyld, Edgardo; Jobe, Alan H; Pillow, J Jane

2015-04-01

Support of the mechanically complex preterm lung needs to facilitate aeration while avoiding ventilation heterogeneities: whether to achieve this gradually or quickly remains unclear. We compared the effect of gradual vs. constant tidal inflations and a pressure-limited sustained inflation (SI) at birth on gas exchange, lung mechanics, gravity-dependent lung volume distribution, and lung injury in 131-day gestation preterm lambs. Lambs were resuscitated with either 1) a 20-s, 40-cmH2O pressure-limited SI (PressSI), 2) a gradual increase in tidal volume (Vt) over 5-min from 3 ml/kg to 7 ml/kg (IncrVt), or 3) 7 ml/kg Vt from birth. All lambs were subsequently ventilated for 15 min with 7 ml/kg Vt with the same end-expiratory pressure. Lung mechanics, gas exchange and spatial distribution of end-expiratory volume (EEV), and tidal ventilation (electrical impedance tomography) were recorded regularly. At 15 min, early mRNA tissue markers of lung injury were assessed. The IncrVt group resulted in greater tissue hysteresivity at 5 min (P = 0.017; two-way ANOVA), higher alveolar-arterial oxygen difference from 10 min (P < 0.01), and least uniform gravity-dependent distribution of EEV. There were no other differences in lung mechanics between groups, and the PressSI and 7 ml/kg Vt groups behaved similarly throughout. EEV was more uniformly distributed, but Vt least so, in the PressSI group. There were no differences in mRNA markers of lung injury. A gradual increase in Vt from birth resulted in less recruitment of the gravity-dependent lung with worse oxygenation. There was no benefit of a SI at birth over mechanical ventilation with 7 ml/kg Vt. Copyright © 2015 the American Physiological Society.

Quantitative evaluation method for nonlinear characteristics of piezoelectric transducers under high stress with complex nonlinear elastic constant

NASA Astrophysics Data System (ADS)

Miyake, Susumu; Kasashima, Takashi; Yamazaki, Masato; Okimura, Yasuyuki; Nagata, Hajime; Hosaka, Hiroshi; Morita, Takeshi

2018-07-01

The high power properties of piezoelectric transducers were evaluated considering a complex nonlinear elastic constant. The piezoelectric LCR equivalent circuit with nonlinear circuit parameters was utilized to measure them. The deformed admittance curve of piezoelectric transducers was measured under a high stress and the complex nonlinear elastic constant was calculated by curve fitting. Transducers with various piezoelectric materials, Pb(Zr,Ti)O3, (K,Na)NbO3, and Ba(Zr,Ti)O3–(Ba,Ca)TiO3, were investigated by the proposed method. The measured complex nonlinear elastic constant strongly depends on the linear elastic and piezoelectric constants. This relationship indicates that piezoelectric high power properties can be controlled by modifying the linear elastic and piezoelectric constants.

The Influence of Fluorocarbon and Hydrocarbon Acyl Groups at the Surface of Bovine Carbonic Anhydrase II on the Kinetics of Denaturation by Sodium Dodecyl Sulfate

PubMed Central

Lee, Andrew; Mirica, Katherine A.; Whitesides, George M.

2011-01-01

This paper examines the influence of acylation of the Lys-ε-NH3+ groups of bovine carbonic anhydrase (BCA, E.C. 4.2.1.1) to Lys-ε-NHCOR (R = -CH3, -CH2CH3, and -CH(CH3)2, -CF3) on the rate of denaturation of this protein in buffer containing sodium dodecyl sulfate (SDS). Analysis of the rates suggested separate effects due to electrostatic charge and hydrophobic interactions. Rates of denaturation (kAc,n) of each series of acylated derivatives depended on the number of acylations (n). Plots of log kAc,n vs. n followed U-shaped curves. Within each series of derivatives, rates of denaturation decreased as n increased to ~7; this decrease was compatible with increasingly unfavorable electrostatic interactions between SDS and protein. In this range of n, rates of denaturation also depended on the choice of the acyl group as n increased to ~7, in a manner compatible with favorable hydrophobic interactions between SDS and the -NHCOR groups. As n increased in the range 7 < n < 14 however, rates of denaturation stayed approximately constant; analysis suggested these rates were compatible with an increasingly important contribution to denaturation that depended both on the net negative charge of the protein and on the hydrophobicity of the R group. The mechanism of denaturation thus seems to change with the extent of acylation of the protein. For derivatives with the same net electrostatic charge, rates of denaturation increased with the acyl group (by a factor of ~3 for n ~ 14) in the order CH3CONH- < CH3CH2CONH- < (CH3)2CHCONH- < CF3CONH-. These results suggested that the hydrophobicity of CF3CONH- is slightly greater (by a factor of < 2) than that of RHCONH- similar in surface area. PMID:21182314

Influence of fluorocarbon and hydrocarbon acyl groups at the surface of bovine carbonic anhydrase II on the kinetics of denaturation by sodium dodecyl sulfate.

PubMed

Lee, Andrew; Mirica, Katherine A; Whitesides, George M

2011-02-10

This paper examines the influence of acylation of the Lys-ε-NH(3)(+) groups of bovine carbonic anhydrase (BCA, EC 4.2.1.1) to Lys-ε-NHCOR (R = -CH(3), -CH(2)CH(3), and -CH(CH(3))(2), -CF(3)) on the rate of denaturation of this protein in buffer containing sodium dodecyl sulfate (SDS). Analysis of the rates suggested separate effects due to electrostatic charge and hydrophobic interactions. Rates of denaturation (k(Ac,n)) of each series of acylated derivatives depended on the number of acylations (n). Plots of log k(Ac,n) vs n followed U-shaped curves. Within each series of derivatives, rates of denaturation decreased as n increased to ∼7; this decrease was compatible with increasingly unfavorable electrostatic interactions between SDS and protein. In this range of n, rates of denaturation also depended on the choice of the acyl group as n increased to ∼7, in a manner compatible with favorable hydrophobic interactions between SDS and the -NHCOR groups. As n increased in the range 7 < n < 14, however, rates of denaturation stayed approximately constant; analysis suggested that these rates were compatible with an increasingly important contribution to denaturation that depended both on the net negative charge of the protein and on the hydrophobicity of the R group. The mechanism of denaturation thus seems to change with the extent of acylation of the protein. For derivatives with the same net electrostatic charge, rates of denaturation increased with the acyl group (by a factor of ∼3 for n ∼ 14) in the order CH(3)CONH- < CH(3)CH(2)CONH- < (CH(3))(2)CHCONH- < CF(3)CONH-. These results suggested that the hydrophobicity of CF(3)CONH- is slightly greater (by a factor of <2) than that of RHCONH- with similar surface area.

Large numbers hypothesis. IV - The cosmological constant and quantum physics

NASA Technical Reports Server (NTRS)

Adams, P. J.

1983-01-01

In standard physics quantum field theory is based on a flat vacuum space-time. This quantum field theory predicts a nonzero cosmological constant. Hence the gravitational field equations do not admit a flat vacuum space-time. This dilemma is resolved using the units covariant gravitational field equations. This paper shows that the field equations admit a flat vacuum space-time with nonzero cosmological constant if and only if the canonical LNH is valid. This allows an interpretation of the LNH phenomena in terms of a time-dependent vacuum state. If this is correct then the cosmological constant must be positive.

Role of endothelium sensitivity to shear stress in noradrenaline-induced constriction of feline femoral arterial bed under constant flow and constant pressure perfusions.

PubMed

Kartamyshev, Sergey P; Balashov, Sergey A; Melkumyants, Arthur M

2007-01-01

The effect of shear stress at the endothelium in the attenuation of the noradrenaline-induced constriction of the femoral vascular bed perfused at a constant blood flow was investigated in 16 anesthetized cats. It is known that the adrenergic vasoconstriction of the femoral vascular bed is considerably greater at a constant pressure perfusion than at a constant blood flow. This difference may depend on the ability of the endothelium to relax smooth muscle in response to an increase in wall shear stress. Since the shear stress is directly related to the blood flow and inversely related to the third power of vessel diameter, vasoconstriction at a constant blood flow increases the wall shear stress that is the stimulus for smooth muscle relaxation opposing constriction. On the other hand, at a constant perfusion pressure, vasoconstriction is accompanied by a decrease in flow rate, which prevents a wall shear stress increase. To reveal the effect of endothelial sensitivity to shear stress, we compared noradrenaline-induced changes in total and proximal arterial resistances during perfusion of the hind limb at a constant blood flow and at a constant pressure in vessels with intact and injured endothelium. We found that in the endothelium-intact bed the same concentration of noradrenaline at a constant flow caused an increase in overall vascular peripheral resistance that was half as large as at a constant perfusion pressure. This difference is mainly confined to the proximal arterial vessels (arteries and large arterioles) whose resistance at a constant flow increased only 0.19 +/- 0.03 times compared to that at a constant pressure. The removal of the endothelium only slightly increased constrictor responses at the perfusion under a constant pressure (noradrenaline-induced increases of both overall and proximal arterial resistance augmented by 12%), while the responses of the proximal vessels at a constant flow became 4.7 +/- 0.4 times greater than in the endothelium-intact bed. A selective blockage of endothelium sensitivity to shear stress using a glutaraldehyde dimer augmented the constrictor responses of the proximal vessels at a constant flow 4.6-fold (+/-0.3), but had no significant effect on the responses at a constant pressure. These results are consistent with the conclusion that the difference in constrictor responses at constant flow and pressure perfusions depends mainly on the smooth muscle relaxation caused by increased wall shear stress. Copyright (c) 2007 S. Karger AG, Basel.

Revised Model of Calcium and Magnesium Binding to the Bacterial Cell Wall

PubMed Central

Thomas, Kieth J.; Rice, Charles V.

2014-01-01

Metals bind to the bacterial cell wall yet the binding mechanisms and affinity constants are not fully understood. The cell wall of gram positive bacteria is characterized by a thick layer of peptidoglycan and anionic teichoic acids anchored in the cytoplasmic membrane (lipoteichoic acid) or covalently bound to the cell wall (wall teichoic acid). The polyphosphate groups of teichoic acid provide one-half of the metal binding sites for calcium and magnesium, contradicting previous reports that calcium binding is 100% dependent on teichoic acid. The remaining binding sites are formed with the carboxyl units of peptidoglycan. In this work we report equilibrium association constants and total metal binding capacities for the interaction of calcium and magnesium ions with the bacterial cell wall. Metal binding is much stronger and previously reported. Curvature of Scatchard plots from the binding data and the resulting two regions of binding affinity suggest the presence of negative cooperative binding, meaning that the binding affinity decreases as more ions become bound to the sample. For Ca2+, Region I has a KA = (1.0 ± 0.2) × 106 M−1 and Region II has a KA = (0.075 ± 0.058) × 106 M−1. For Mg2+, KA1 = (1.5 ± 0.1) × 106 and KA2 = (0.17 ± 0.10) × 106. A binding capacity (η) is reported for both regions. However, since binding is still occurring in Region II, the total binding capacity is denoted by η2, which are 0.70 ± 0.04 µmol/mg and 0.67 ± 0.03 µmol/mg for Ca2+ and Mg2+ respectively. These data contradict the current paradigm of there being a single metal affinity value that is constant over a range of concentrations. We also find that measurement of equilibrium binding constants is highly sample dependent, suggesting a role for diffusion of metals through heterogeneous cell wall fragments. As a result, we are able to reconcile many contradictory theories that describe binding affinity and the binding mode of divalent metal cations. PMID:25315444

Optical parametric amplifiers using chirped quasi-phase-matching gratings I: practical design formulas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Charbonneau-Lefort, Mathieu; Afeyan, Bedros; Fejer, M. M.

Optical parametric amplifiers using chirped quasi-phase-matching (QPM) gratings offer the possibility of engineering the gain and group delay spectra. We give practical formulas for the design of such amplifiers. We consider linearly chirped QPM gratings providing constant gain over a broad bandwidth, sinusoidally modulated profiles for selective frequency amplification and a pair of QPM gratings working in tandem to ensure constant gain and constant group delay at the same time across the spectrum. Finally, the analysis is carried out in the frequency domain using Wentzel–Kramers–Brillouin analysis.

Effect of temperature on the protonation of N-(2-hydroxyethyl)ethylenediamine-N,N',N'-triacetic acid in aqueous solutions: Potentiometric and calorimetric studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Xingliang; Zhang, Zhicheng; Endrizzi, Francesco

2015-06-01

The TALSPEAK process (Trivalent Actinide Lanthanide Separations by Phosphorus-reagent Extraction from Aqueous Komplexes) has been demonstrated in several pilot-scale operations to be effective at separating trivalent actinides (An 3+) from trivalent lanthanides (Ln 3+). However, fundamental studies have revealed undesired aspects of TALSPEAK, such as the significant partitioning of Na +, lactic acid, and water into the organic phase, thermodynamically unpredictable pH dependence, and the slow extraction kinetics. In the modified TALSPEAK process, the combination of the aqueous holdback complexant HEDTA (N-(2-hydroxyethyl)ethylenediamine-N,N',N'-triacetic acid) with the extractant HEH[EHP] (2-ethyl(hexyl) phosphonic acid mono-2-ethylhexyl ester) in the organic phase has been found tomore » exhibit a nearly flat pH dependence between 2.5 and 4.5 and more rapid phase transfer kinetics for the heavier lanthanides. To help understand the speciation of Ln 3+ and An 3+ in the modified TALSPEAK, systematic studies are underway on the thermodynamics of major reactions in the HEDTA system under conditions relevant to the process (e.g., higher temperatures). Thermodynamics of the protonation and complexation of HEDTA with Ln 3+ were studied at variable temperatures. Equilibrium constants and enthalpies were determined by a combination of techniques including potentiometry and calorimetry. This paper presents the protonation constants of HEDTA at T = (25 to 70) °C. The potentiometric titrations have demonstrated that, stepwise, the first two protonation constants decrease and the third one slightly increases with the increase of temperature. This trend is in good agreement with the enthalpy of protonation directly determined by calorimetry. The results of NMR analysis further confirm that the first two protonation reactions occur on the diamine nitrogen atoms, while the third protonation reaction occurs on the oxygen of a carboxylate group. These data, in conjunction with the thermodynamic parameters of Ln 3+/An 3+ complexes with HEDTA at different temperatures, will help to predict the speciation and temperature-dependent behavior of Ln 3+/An 3+ in the modified TALSPEAK process.« less

Partial repair in irreparable rotator cuff tear: our experience in long-term follow-up.

PubMed

Di Benedetto, E D; Di Benedetto, Paolo; Fiocchi, Andrea; Beltrame, Alessandro; Causero, Araldo

2017-10-18

Massive rotator cuff tears are a common source of shoulder pain and dysfunction, especially in middle age patient; these lesions represent about 20% of all rotator cuff tears and 80% of recurrent tears. Some lesions are not repairable or should not be repaired: in this case, a rotator cuff partial repair should be recommended. The aim of the study is to evaluate the outcome of rotator cuff partial repair in irreparable rotator cuff massive tear at medium and long-term follow-up. We have evaluated 74 consecutive patients treated with functional repair of rotator cuff by the same surgeon between 2006 and 2014. We divided patients into 2 groups, obtaining 2 average follow-up: at about 6,5 (group A) and 3 years (group B). In December 2015, we evaluated in every patient ROM and Constant Score. We analyzed difference between pre-operatory data and the 2 groups.  Results: We found statistical significant difference in ROM and in Constant Score between pre-operatory data and group A and group B. Between group A and group B there is relevant difference in Constant Score but not in ROM. Partial repair can give good results in a medium follow-up, in terms of pain relief and improvement of ROM, as well as in quality of life. Difference in ROM and Constant Score between group A and group B may indicate the begin of partial repair failure; according to our data, 6-7 years may be the time limit for this surgery technique.

Teaching Nanochemistry: Madelung Constants of Nanocrystals

ERIC Educational Resources Information Center

Baker, Mark D.; Baker, A. David

2010-01-01

The Madelung constants for binary ionic nanoparticles are determined. The computational method described here sums the Coulombic interactions of each ion in the particle without the use of partial charges commonly used for bulk materials. The results show size-dependent lattice energies. This is a useful concept in teaching how properties such as…

Ground State of the Universe and the Cosmological Constant. A Nonperturbative Analysis.

PubMed

Husain, Viqar; Qureshi, Babar

2016-02-12

The physical Hamiltonian of a gravity-matter system depends on the choice of time, with the vacuum naturally identified as its ground state. We study the expanding Universe with scalar field in the volume time gauge. We show that the vacuum energy density computed from the resulting Hamiltonian is a nonlinear function of the cosmological constant and time. This result provides a new perspective on the relation between time, the cosmological constant, and vacuum energy.

Local-duality QCD sum rules for strong isospin breaking in the decay constants of heavy-light mesons.

PubMed

Lucha, Wolfgang; Melikhov, Dmitri; Simula, Silvano

2018-01-01

We discuss the leptonic decay constants of heavy-light mesons by means of Borel QCD sum rules in the local-duality (LD) limit of infinitely large Borel mass parameter. In this limit, for an appropriate choice of the invariant structures in the QCD correlation functions, all vacuum-condensate contributions vanish and all nonperturbative effects are contained in only one quantity, the effective threshold. We study properties of the LD effective thresholds in the limits of large heavy-quark mass [Formula: see text] and small light-quark mass [Formula: see text]. In the heavy-quark limit, we clarify the role played by the radiative corrections in the effective threshold for reproducing the pQCD expansion of the decay constants of pseudoscalar and vector mesons. We show that the dependence of the meson decay constants on [Formula: see text] arises predominantly (at the level of 70-80%) from the calculable [Formula: see text]-dependence of the perturbative spectral densities. Making use of the lattice QCD results for the decay constants of nonstrange and strange pseudoscalar and vector heavy mesons, we obtain solid predictions for the decay constants of heavy-light mesons as functions of [Formula: see text] in the range from a few to 100 MeV and evaluate the corresponding strong isospin-breaking effects: [Formula: see text], [Formula: see text], [Formula: see text], [Formula: see text].

Structural phase transition of as-synthesized Sr-Mn nanoferrites by annealing temperature

NASA Astrophysics Data System (ADS)

Amer, M. A.; Meaz, T. M.; Attalah, S. S.; Ghoneim, A. I.

2015-11-01

The Sr0.2Mn0.8Fe2O4 nanoparticle ferrites were synthesized by the co-precipitation method and annealed at different temperatures T. XRD, TEM, FT-IR, VSM and Mössbauer techniques were used to characterize the samples. This study proved that the structural phase of nanoferrites was transformed from cubic spinel for T≤500 °C to Z-type hexagonal for T≥700 °C. The structural transformation was attributed to Jahn-Teller effect of the Mn3+ ions and/or atomic disorder existed in the crystal lattice. The obtained spectra and parameters for the samples were affected by the transformation process. The lattice constant a showed a splitting to a and c for T>500 °C. The lattice constant c, grain and crystallite size R, strain, octahedral B-site band position and force constant, Debye temperature, coercivity Hc, remnant magnetization, squareness and magnetic moment, spontaneous magnetization and hyperfine magnetic fields showed increase against T. The lattice constant a, distortion and dislocation parameters, specific surface area, tetrahedral A-site band position and force constant, threshold frequency, Young's and bulk moduli, saturation magnetization Ms, area ratio of B-/A-sites, A-site line width were decreased with T. Experimental and theoretical densities, porosity, Poison ratio, stiffness constants, rigidity modulus, B-site line width and spontaneous magnetization showed dependence on T, whereas Ms and Hc proved dependence on R.

Temperature-dependent inotropic and lusitropic indices based on half-logistic time constants for four segmental phases in isovolumic left ventricular pressure-time curve in excised, cross-circulated canine heart.

PubMed

Mizuno, Ju; Mohri, Satoshi; Yokoyama, Takeshi; Otsuji, Mikiya; Arita, Hideko; Hanaoka, Kazuo

2017-02-01

Varying temperature affects cardiac systolic and diastolic function and the left ventricular (LV) pressure-time curve (PTC) waveform that includes information about LV inotropism and lusitropism. Our proposed half-logistic (h-L) time constants obtained by fitting using h-L functions for four segmental phases (Phases I-IV) in the isovolumic LV PTC are more useful indices for estimating LV inotropism and lusitropism during contraction and relaxation periods than the mono-exponential (m-E) time constants at normal temperature. In this study, we investigated whether the superiority of the goodness of h-L fits remained even at hypothermia and hyperthermia. Phases I-IV in the isovolumic LV PTCs in eight excised, cross-circulated canine hearts at 33, 36, and 38 °C were analyzed using h-L and m-E functions and the least-squares method. The h-L and m-E time constants for Phases I-IV significantly shortened with increasing temperature. Curve fitting using h-L functions was significantly better than that using m-E functions for Phases I-IV at all temperatures. Therefore, the superiority of the goodness of h-L fit vs. m-E fit remained at all temperatures. As LV inotropic and lusitropic indices, temperature-dependent h-L time constants could be more useful than m-E time constants for Phases I-IV.

Impact of topology in foliated quantum Einstein gravity.

PubMed

Houthoff, W B; Kurov, A; Saueressig, F

2017-01-01

We use a functional renormalization group equation tailored to the Arnowitt-Deser-Misner formulation of gravity to study the scale dependence of Newton's coupling and the cosmological constant on a background spacetime with topology [Formula: see text]. The resulting beta functions possess a non-trivial renormalization group fixed point, which may provide the high-energy completion of the theory through the asymptotic safety mechanism. The fixed point is robust with respect to changing the parametrization of the metric fluctuations and regulator scheme. The phase diagrams show that this fixed point is connected to a classical regime through a crossover. In addition the flow may exhibit a regime of "gravitational instability", modifying the theory in the deep infrared. Our work complements earlier studies of the gravitational renormalization group flow on a background topology [Formula: see text] (Biemans et al. Phys Rev D 95:086013, 2017, Biemans et al. arXiv:1702.06539, 2017) and establishes that the flow is essentially independent of the background topology.

Biotransformation of trace organic chemicals during groundwater recharge: How useful are first-order rate constants?

PubMed

Regnery, J; Wing, A D; Alidina, M; Drewes, J E

2015-08-01

This study developed relationships between the attenuation of emerging trace organic chemicals (TOrC) during managed aquifer recharge (MAR) as a function of retention time, system characteristics, and operating conditions using controlled laboratory-scale soil column experiments simulating MAR. The results revealed that MAR performance in terms of TOrC attenuation is primarily determined by key environmental parameters (i.e., redox, primary substrate). Soil columns with suboxic and anoxic conditions performed poorly (i.e., less than 30% attenuation of moderately degradable TOrC) in comparison to oxic conditions (on average between 70-100% attenuation for the same compounds) within a residence time of three days. Given this dependency on redox conditions, it was investigated if key parameter-dependent rate constants are more suitable for contaminant transport modeling to properly capture the dynamic TOrC attenuation under field-scale conditions. Laboratory-derived first-order removal kinetics were determined for 19 TOrC under three different redox conditions and rate constants were applied to MAR field data. Our findings suggest that simplified first-order rate constants will most likely not provide any meaningful results if the target compounds exhibit redox dependent biotransformation behavior or if the intention is to exactly capture the decline in concentration over time and distance at field-scale MAR. However, if the intention is to calculate the percent removal after an extended time period and subsurface travel distance, simplified first-order rate constants seem to be sufficient to provide a first estimate on TOrC attenuation during MAR. Copyright © 2015 Elsevier B.V. All rights reserved.

Solvent dielectric effect and side chain mutation on the structural stability of Burkholderia cepacia lipase active site: a quantum mechanical/molecular mechanics study.

PubMed

Tahan, A; Monajjemi, M

2011-12-01

Quantum mechanical and molecular dynamics methods were used to analyze the structure and stability of neutral and zwitterionic configurations of the extracted active site sequence from a Burkholderia cepacia lipase, histidyl-seryl-glutamin (His86-Ser87-Gln88) and its mutated form, histidyl-cysteyl-glutamin (His86-Cys87-Gln88) in vacuum and different solvents. The effects of solvent dielectric constant, explicit and implicit water molecules and side chain mutation on the structure and stability of this sequence in both neutral and zwitterionic forms are represented. The quantum mechanics computations represent that the relative stability of zwitterionic and neutral configurations depends on the solvent structure and its dielectric constant. Therefore, in vacuum and the considered non-polar solvents, the neutral form of the interested sequences is more stable than the zwitterionic form, while their zwitterionic form is more stable than the neutral form in the aqueous solution and the investigated polar solvents in most cases. However, on the potential energy surfaces calculated, there is a barrier to proton transfer from the positively charged ammonium group to the negatively charged carboxylat group or from the ammonium group to the adjacent carbonyl oxygen and or from side chain oxygen and sulfur to negatively charged carboxylat group. Molecular dynamics simulations (MD) were also performed by using periodic boundary conditions for the zwitterionic configuration of the hydrated molecules in a box of water molecules. The obtained results demonstrated that the presence of explicit water molecules provides the more compact structures of the studied molecules. These simulations also indicated that side chain mutation and replacement of sulfur with oxygen leads to reduction of molecular flexibility and packing.

Period gene expression in four neurons is sufficient for rhythmic activity of Drosophila melanogaster under dim light conditions.

PubMed

Rieger, Dirk; Wülbeck, Corinna; Rouyer, Francois; Helfrich-Förster, Charlotte

2009-08-01

The clock gene expressing lateral neurons (LN) is crucial for Drosophila 's rhythmic locomotor activity under constant conditions. Among the LN, the PDF expressing small ventral lateral neurons (s-LN(v)) are thought to control the morning activity of the fly (M oscillators) and to drive rhythmic activity under constant darkness. In contrast, a 5th PDF-negative s-LN( v) and the dorsal lateral neurons (LN(d)) appeared to control the fly's evening activity (E oscillators) and to drive rhythmic activity under constant light. Here, the authors restricted period gene expression to 4 LN-the 5th s-LN(v) and 3 LN(d)- that are all thought to belong to the E oscillators and tested them in low light conditions. Interestingly, such flies showed rather normal bimodal activity patterns under light moonlight and constant moonlight conditions, except that the phase of M and E peaks was different. This suggests that these 4 neurons behave as ''M'' and ''E'' cells in these conditions. Indeed, they found by PER and TIM immunohistochemistry that 2 LN(d) advanced their phase upon moonlight as predicted for M oscillators, whereas the 5th s-LN(v) and 1 LN(d) delayed their activity upon moonlight as predicted for E oscillators. Their results suggest that the M or E characteristic of clock neurons is rather flexible. M and E oscillator function may not be restricted to certain anatomically defined groups of clock neurons but instead depends on the environmental conditions.

Zero-point corrections and temperature dependence of HD spin-spin coupling constants of heavy metal hydride and dihydrogen complexes calculated by vibrational averaging.

PubMed

Mort, Brendan C; Autschbach, Jochen

2006-08-09

Vibrational corrections (zero-point and temperature dependent) of the H-D spin-spin coupling constant J(HD) for six transition metal hydride and dihydrogen complexes have been computed from a vibrational average of J(HD) as a function of temperature. Effective (vibrationally averaged) H-D distances have also been determined. The very strong temperature dependence of J(HD) for one of the complexes, [Ir(dmpm)Cp*H2]2 + (dmpm = bis(dimethylphosphino)methane) can be modeled simply by the Boltzmann average of the zero-point vibrationally averaged JHD of two isomers. For this complex and four others, the vibrational corrections to JHD are shown to be highly significant and lead to improved agreement between theory and experiment in most cases. The zero-point vibrational correction is important for all complexes. Depending on the shape of the potential energy and J-coupling surfaces, for some of the complexes higher vibrationally excited states can also contribute to the vibrational corrections at temperatures above 0 K and lead to a temperature dependence. We identify different classes of complexes where a significant temperature dependence of J(HD) may or may not occur for different reasons. A method is outlined by which the temperature dependence of the HD spin-spin coupling constant can be determined with standard quantum chemistry software. Comparisons are made with experimental data and previously calculated values where applicable. We also discuss an example where a low-order expansion around the minimum of a complicated potential energy surface appears not to be sufficient for reproducing the experimentally observed temperature dependence.

Molecular mobility, morphology, and ion conduction in ionomers for electroactive devices

NASA Astrophysics Data System (ADS)

Tudryn, Gregory J.

A sequential study of ion-containing polymers capable of ion solvation with varied ion content, dielectric constant, and counterions is presented in this dissertation in order to compare ion transport properties in ionomers with various ionic interactions. Structure-property relationships in these ion containing polymers are defined using x-ray scattering, rheology and dielectric spectroscopy, enabling the quantification of ion transport dynamics. Poly(ethylene oxide), (PEO) based ionomers are investigated in order to probe the relation between ion conduction and segmental relaxation, and copolymers of PEO and Poly(tetramethylene oxide), (PTMO) further develop an understanding of the trade-off between ion solvation and segmental dynamics. Ionomers with ionic liquid counterions probe diffuse charge interactions and steric effects on ion transport, and incorporation of ionic liquids into ionomer membranes such as Nafion provides desirable thermal and ion conducting properties which extend the use of such membranes for electroactive devices. PEO ionomers exhibit a strong relation between ionic conductivity and segmental dynamics, providing insight that the glass transition temperature, Tg, dominates the ion conduction mechanism. Increasing temperature induces aggregation of ionic groups as evidenced by the static dielectric constant and X-ray scattering as a function of temperature, revealing the contribution of ionic dipoles in the measured dielectric constant. The trade-off between ion solvation and fast polymer segmental dynamics are quantified in copolymer ionomers of PEO and lower Tg PTMO. While conducting ion content remains nearly unchanged, conductivity is lowered upon incorporation of PTMO, because the vast majority of the PTMO microphase separates from the PEO-rich microdomain that remains continuous and contributes most of the ion conduction. Dielectric constants and X-ray scattering show consistent changes with temperature that suggest a cascading aggregation process in Na ionomers as ionic dipoles thermally randomize and lower the measured dielectric constant of the medium, leading to further aggregation. We observe amplified microphase-separation through ionic groups preferentially solvated by PEO chains, as seen in block copolymers with added salt. Even at 25%PEO / 75%PTMO the ionomers have VFT temperature dependence of conducting ion mobility, meaning that the 25% PEO/ion microphase is still continuous A model is developed to describe the frequency dependent storage and loss modulus and the delay in Rouse motion due to ion association lifetime, as functions of ion content and molecular weight for our low molecular weight ionomers. The ion rearrangement relaxation in dielectric spectroscopy is clearly the ion association lifetime that controls terminal dynamics in linear viscoelasticity, allowing a simple sticky Rouse model, using the most-probable distribution based on NMR Mn, to fully describe master curves of the frequency dependent storage and loss modulus. Using insight from ionic interaction strength, ionic liquids are used as counterions, effectively plasticizing the ionomers without added solvent. Ionic interactions were weakened with increasing counterion size, and with modification of cations using ether-oxygen, promoting self-solvation, which increases conducting ion density by an order of magnitude. Room temperature ionic liquids were subsequently used in combination with NafionRTM membranes as electroactive substrates to correlate ion transport to morphology as a function of volume fraction of ionic liquid. This study illuminated the critical volume uptake of ionic liquid in Nafion, identifying percolation of ionic pathways and a significant increase in dielectric constant at low frequencies, indicating an increase in the number density of ions capable of polarizing at the electrode surface. Consequently, the fundamental information obtained about the structure-property relations of ionomers can be used to predict and design advanced ion-containing polymers to be used in battery membranes and a variety of electroactive devices, including actuators and electromechanical sensors.

Laser flash photolysis of ozone - O/1D/ quantum yields in the fall-off region 297-325 nm

NASA Technical Reports Server (NTRS)

Brock, J. C.; Watson, R. T.

1980-01-01

The wavelength dependence of the quantum yield for O(1D) production from ozone photolysis has been determined between 297.5 nm and 325 nm in order to resolve serious discrepancies among previous studies. The results of this investigation are compared to earlier work by calculating atmospheric production rate constants for O(1D). It is found that for the purpose of calculating this rate constant, there is now good agreement among three studies at 298 K. Furthermore, it appears that previous data on the temperature dependence of the O(1D) quantum yield fall-off is adequate for determining the vertical profile of the O(1D) production rate constant. Several experimental difficulties associated with using NO2(asterisk) chemiluminescence to monitor O(1D) have been identified.

Absolute rate constant for the O plus NO chemiluminescence in the near infrared

NASA Technical Reports Server (NTRS)

Golde, M. F.; Roche, A. E.; Kaufman, F.

1973-01-01

Infrared chemiluminescence from the process O + NO (+M) NO2 + hv (+M) has been studied between 1.3 and 4.1 micrometer. The wavelength dependence of the continuum between 1.3 and 3.3 micrometer is in fair agreement with previous studies and the measured radiative rate constant at 1.51 micrometer establishes the NO-O glow in this spectral range as a secondary emission standard. Comparison with previous studies of the visible region of the glow implies that the overall radiative rate constant lies in the range (9.4 to 11.2) x 10 to the minus 17 power cu cm sec/1. In the region 3.3 to 4.1 micrometer, the previously observed broad band, peaking at 3.7 micrometer, shows a complex kinetic dependence on O and M.

Bond-strength inversion in (In,Ga)As semiconductor alloys

NASA Astrophysics Data System (ADS)

Eckner, Stefanie; Ritter, Konrad; Schöppe, Philipp; Haubold, Erik; Eckner, Erich; Rensberg, Jura; Röder, Robert; Ridgway, Mark C.; Schnohr, Claudia S.

2018-05-01

The atomic-scale structure and vibrational properties of semiconductor alloys are determined by the energy required for stretching and bending the individual bonds. Using temperature-dependent extended x-ray absorption fine-structure spectroscopy, we have determined the element-specific In-As and Ga-As effective bond-stretching force constants in (In,Ga)As as a function of the alloy composition. The results reveal a striking inversion of the bond strength where the originally stiffer bond in the parent materials becomes the softer bond in the alloy and vice versa. Our findings clearly demonstrate that changes of both the individual bond length and the surrounding matrix affect the bond-stretching force constants. We thus show that the previously used common assumptions about the element-specific force constants in semiconductor alloys do not reproduce the composition dependence determined experimentally for (In,Ga)As.

Assessing localized skin-to-fat water in arms of women with breast cancer via tissue dielectric constant measurements in pre- and post-surgery patients.

PubMed

Mayrovitz, Harvey N; Weingrad, Daniel N; Lopez, Lidice

2015-05-01

Skin-to-fat tissue dielectric constant (TDC) values at 300 MHz largely depend on tissue water and provide a rapid way to assess skin water by touching skin with a probe for approximately 10 s. This method has been used to investigate lymphedema features accompanying breast cancer (BC), but relationships between TDC and nodes removed or symptoms is unclear. Our goals were: (1) to compare TDC values in BC patients prior to surgery (group A) and in patients who had BC-related surgery (group B) to determine if TDC of group B were related to nodes removed and reported symptoms and (2) to develop tentative lymphedema-detection thresholds. Arm volumes and TDC values of at-risk and contralateral forearms and biceps were determined in 103 women awaiting surgery for BC and 104 women who had BC-related surgery 26.3 ± 17.5 months prior to evaluation. Inter-arm ratios (at-risk/contralateral) were determined and patients answered questions about lymphedema-related symptoms. Inter-arm TDC ratios for group A forearm and biceps were respectively 1.003 ± 0.096 and 1.012 ± 0.143. Group B forearm ratios were significantly greater, and among group B patients who reported at least one symptom there was a significant correlation between TDC ratios and symptom burden and nodes removed. Inter-arm TDC ratios are significantly related to symptoms and nodes removed. Ratios increase with increasing symptom score and might be used to detect pre-clinical unilateral lymphedema using TDC ratio thresholds of 1.30 for forearm and 1.45 for biceps. Threshold confirmation awaits targeted prospective studies but can serve as guideposts to provide quantitative and easily done tracking assessments during follow-up visits.

Perception of coarticulated tones by non-native listeners

NASA Astrophysics Data System (ADS)

Bent, Tessa

2005-04-01

Mandarin lexical tones vary in their acoustic realization depending on the surrounding context. Native listeners compensate for this tonal coarticulation when identifying tones in context. This study investigated how native English listeners handle tonal coarticulation by testing native English and Mandarin listeners discrimination of the four Mandarin lexical tones in tri-syllabic sequences in which the middle tone varied while the first and last tones were held constant. Three different such frames were tested. As expected, Mandarin listeners discriminated all pairs in all contexts with a high degree of accuracy. English listeners exhibited poorer discrimination than Mandarin listeners and their discrimination accuracy showed a high degree of context dependency. In addition to assessing accuracy, reactions times to correctly discriminated different trials were entered into a multidimensional scaling analysis. For both listener groups, the arrangement of tones in perceptual space varied depending on the surrounding context suggesting that listeners attend to different acoustic attributes of the target tone depending on the surrounding tones. These results demonstrate the importance for models of cross-language speech perception of including contextual variation when characterizing the perception of non-native prosodic categories. [Work supported by NIH/NIDCD

Simple Model for Detonation Energy and Rate

NASA Astrophysics Data System (ADS)

Lauderbach, Lisa M.; Souers, P. Clark

2017-06-01

A simple model is used to derive the Eyring equation for the size effect and detonation rate, which depends on a constant energy density. The rate derived from detonation velocities is then converted into a rate constant to be used in a reactive flow model. The rate might be constant if the size effect curve is straight, but the rate constant will change with the radius of the sample and cannot be a constant. This is based on many careful cylinder tests have been run recently on LX-17 with inner copper diameters ranging from 12.7 to 101.6 mm. Copper wall velocities at scaled displacements of 6, 12.5 and 19 mm equate to values at relative volumes of 2.4, 4.4 and 7.0. At each point, the velocities from 25.4 to 101.6 mm are constant within error whereas the 12.7 mm velocities are lower. Using the updated Gurney model, the energy densities at the three larger sizes are also constant. Similar behavior has been seen in LX-14, LX-04, and an 83% RDX mix. A rough saturation has also been in old ANFO data for diameters of 101.6 mm and larger. Although the energy densities saturate, the detonation velocities continue to increase with size. These observations suggest that maximum energy density is a constant for a given explosive of a given density. The correlation of energy density with detonation velocity is not good because the latter depends on the total energy of the sample. This work performed under the auspices of the U. S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

Theoretical rate constants of super-exchange hole transfer and thermally induced hopping in DNA.

PubMed

Shimazaki, Tomomi; Asai, Yoshihiro; Yamashita, Koichi

2005-01-27

Recently, the electronic properties of DNA have been extensively studied, because its conductivity is important not only to the study of fundamental biological problems, but also in the development of molecular-sized electronics and biosensors. We have studied theoretically the reorganization energies, the activation energies, the electronic coupling matrix elements, and the rate constants of hole transfer in B-form double-helix DNA in water. To accommodate the effects of DNA nuclear motions, a subset of reaction coordinates for hole transfer was extracted from classical molecular dynamics (MD) trajectories of DNA in water and then used for ab initio quantum chemical calculations of electron coupling constants based on the generalized Mulliken-Hush model. A molecular mechanics (MM) method was used to determine the nuclear Franck-Condon factor. The rate constants for two types of mechanisms of hole transfer-the thermally induced hopping (TIH) and the super-exchange mechanisms-were determined based on Marcus theory. We found that the calculated matrix elements are strongly dependent on the conformations of the nucleobase pairs of hole-transferable DNA and extend over a wide range of values for the "rise" base-step parameter but cluster around a particular value for the "twist" parameter. The calculated activation energies are in good agreement with experimental results. Whereas the rate constant for the TIH mechanism is not dependent on the number of A-T nucleobase pairs that act as a bridge, the rate constant for the super-exchange process rapidly decreases when the length of the bridge increases. These characteristic trends in the calculated rate constants effectively reproduce those in the experimental data of Giese et al. [Nature 2001, 412, 318]. The calculated rate constants were also compared with the experimental results of Lewis et al. [Nature 2000, 406, 51].

Echolocating Big Brown Bats, Eptesicus fuscus, Modulate Pulse Intervals to Overcome Range Ambiguity in Cluttered Surroundings

PubMed Central

Wheeler, Alyssa R.; Fulton, Kara A.; Gaudette, Jason E.; Simmons, Ryan A.; Matsuo, Ikuo; Simmons, James A.

2016-01-01

Big brown bats (Eptesicus fuscus) emit trains of brief, wideband frequency-modulated (FM) echolocation sounds and use echoes of these sounds to orient, find insects, and guide flight through vegetation. They are observed to emit sounds that alternate between short and long inter-pulse intervals (IPIs), forming sonar sound groups. The occurrence of these strobe groups has been linked to flight in cluttered acoustic environments, but how exactly bats use sonar sound groups to orient and navigate is still a mystery. Here, the production of sound groups during clutter navigation was examined. Controlled flight experiments were conducted where the proximity of the nearest obstacles was systematically decreased while the extended scene was kept constant. Four bats flew along a corridor of varying widths (100, 70, and 40 cm) bounded by rows of vertically hanging plastic chains while in-flight echolocation calls were recorded. Bats shortened their IPIs for more rapid spatial sampling and also grouped their sounds more tightly when flying in narrower corridors. Bats emitted echolocation calls with progressively shorter IPIs over the course of a flight, and began their flights by emitting shorter starting IPI calls when clutter was denser. The percentage of sound groups containing 3 or more calls increased with increasing clutter proximity. Moreover, IPI sequences having internal structure become more pronounced when corridor width narrows. A novel metric for analyzing the temporal organization of sound sequences was developed, and the results indicate that the time interval between echolocation calls depends heavily on the preceding time interval. The occurrence of specific IPI patterns were dependent upon clutter, which suggests that sonar sound grouping may be an adaptive strategy for coping with pulse-echo ambiguity in cluttered surroundings. PMID:27445723

Search for ionisation density effects in the radiation absorption stage in LiF:Mg,Ti.

PubMed

Nail, I; Horowitz, Y S; Oster, L; Brandan, M E; Rodríguez-Villafuerte, M; Buenfil, A E; Ruiz-Trejo, C; Gamboa-Debuen, I; Avila, O; Tovar, V M; Olko, P; Ipe, N

2006-01-01

Optical absorption (OA) dose-response of LiF:Mg,Ti (TLD-100) is studied as a function of electron energy (ionisation density) and irradiation dose. Contrary to the situation in thermoluminescence dose-response where the supralinearity is strongly energy-dependent, no dependence of the OA dose filling constants on energy is observed. This result is interpreted as indicating a lack of competitive process in the radiation absorption stage. The lack of an energy dependence of the dose filling constant also suggests that the charge carrier migration distances are sufficiently large to smear out the differences in the non-uniform distribution of ionisation events created by the impinging gamma/electron radiation of various energies.

Anatomy of the magnetic catalysis by renormalization-group method

NASA Astrophysics Data System (ADS)

Hattori, Koichi; Itakura, Kazunori; Ozaki, Sho

2017-12-01

We first examine the scaling argument for a renormalization-group (RG) analysis applied to a system subject to the dimensional reduction in strong magnetic fields, and discuss the fact that a four-Fermi operator of the low-energy excitations is marginal irrespective of the strength of the coupling constant in underlying theories. We then construct a scale-dependent effective four-Fermi interaction as a result of screened photon exchanges at weak coupling, and establish the RG method appropriately including the screening effect, in which the RG evolution from ultraviolet to infrared scales is separated into two stages by the screening-mass scale. Based on a precise agreement between the dynamical mass gaps obtained from the solutions of the RG and Schwinger-Dyson equations, we discuss an equivalence between these two approaches. Focusing on QED and Nambu-Jona-Lasinio model, we clarify how the properties of the interactions manifest themselves in the mass gap, and point out an importance of respecting the intrinsic energy-scale dependences in underlying theories for the determination of the mass gap. These studies are expected to be useful for a diagnosis of the magnetic catalysis in QCD.

Solitons and the energy-momentum tensor for affine Toda theory

NASA Astrophysics Data System (ADS)

Olive, D. I.; Turok, N.; Underwood, J. W. R.

1993-07-01

Following Leznov and Saveliev, we present the general solution to Toda field theories of conformal, affine or conformal affine type, associated with a simple Lie algebra g. These depend on a free massless field and on a group element. By putting the former to zero, soliton solutions to the affine Toda theories with imaginary coupling constant result with the soliton data encoded in the group element. As this requires a reformulation of the affine Kac-Moody algebra closely related to that already used to formulate the physical properties of the particle excitations, including their scattering matrices, a unified treatment of particles and solitons emerges. The physical energy—momentum tensor for a general solution is broken into a total derivative plus a part dependent only on the derivatives of the free field. Despite the non-linearity of the field equations and their complex nature the energy and momentum of the N-soliton solution is shown to be real, equalling the sum of contributions from the individual solitons. There are rank-g species of soliton, with masses given by a generalisation of a formula due to Hollowood, being proportional to the components of the left Perron-Frobenius eigenvector of the Cartan matrix of g.

Self-Esteem and the Cultural Trade-off: Evidence for the Role of Individualism-Collectivism.

ERIC Educational Resources Information Center

Tafarodi, Romin W.; Smith, Alyson J.; Lang, James M.

1999-01-01

Compared Malaysian (collectivist) and British (individualist) students on their self-liking and self-competence. Malaysians were lower in self-competence when self-liking was held constant but were higher in self-liking when self-competence was held constant. Differences between groups were not reliable after statistically equating groups on two…

Field Dependence-Independence and Physical Activity Engagement among Middle School Students

ERIC Educational Resources Information Center

Liu, Wenhao; Chepyator-Thomson, Jepkorir Rose

2009-01-01

Background: Field dependence-independence (FDI) is a tendency to rely on external frames (given situations and authoritative people) or internal frames (oneself, including one's own body) for one's information processing and behavior. Literature has constantly reported that field-dependent (FD) individuals, who are less autonomous in…

Anharmonic Potential Constants and Their Dependence Upon Bond Length

DOE R&D Accomplishments Database

Herschbach, D. R.; Laurie, V. W.

1961-01-01

Empirical study of cubic and quartic vibrational force constants for diatomic molecules shows them to be approximately exponential functions of internuclear distance. A family of curves is obtained, determined by the location of the bonded atoms in rows of the periodic table. Displacements between successive curves correspond closely to those in Badger's rule for quadratic force constants (for which the parameters are redetermined to accord with all data now available). Constants for excited electronic and ionic states appear on practically the same curves as those for the ground states. Predictions based on the diatomic correlations agree with the available cubic constants for bond stretching in polyatomic molecules, regardless of the type of bonding involved. Implications of these regularities are discussed. (auth)

NoSOCS in SDSS - VI. The environmental dependence of AGN in clusters and field in the local Universe

NASA Astrophysics Data System (ADS)

Lopes, P. A. A.; Ribeiro, A. L. B.; Rembold, S. B.

2017-11-01

We investigated the variation in the fraction of optical active galactic nuclei (AGNs) hosts with stellar mass, as well as their local and global environments. Our sample is composed of cluster members and field galaxies at z ≤ 0.1 and we consider only strong AGN. We find a strong variation in the AGN fraction (FAGN) with stellar mass. The field population comprises a higher AGN fraction compared to the global cluster population, especially for objects with log M* > 10.6. Hence, we restricted our analysis to more massive objects. We detected a smooth variation in the FAGN with local stellar mass density for cluster objects, reaching a plateau in the field environment. As a function of cluster-centric distance we verify that FAGN is roughly constant for R > R200, but show a steep decline inwards. We have also verified the dependence of the AGN population on cluster velocity dispersion, finding a constant behaviour for low mass systems (σP ≲ 650-700 km s-1). However, there is a strong decline in FAGN for higher mass clusters (>700 km s-1). When comparing the FAGN in clusters with or without substructure, we only find different results for objects at large radii (R > R200), in the sense that clusters with substructure present some excess in the AGN fraction. Finally, we have found that the phase-space distribution of AGN cluster members is significantly different than other populations. Due to the environmental dependence of FAGN and their phase-space distribution, we interpret AGN to be the result of galaxy interactions, favoured in environments where the relative velocities are low, typical of the field, low mass groups or cluster outskirts.

A new variable interval schedule with constant hazard rate and finite time range.

PubMed

Bugallo, Mehdi; Machado, Armando; Vasconcelos, Marco

2018-05-27

We propose a new variable interval (VI) schedule that achieves constant probability of reinforcement in time while using a bounded range of intervals. By sampling each trial duration from a uniform distribution ranging from 0 to 2 T seconds, and then applying a reinforcement rule that depends linearly on trial duration, the schedule alternates reinforced and unreinforced trials, each less than 2 T seconds, while preserving a constant hazard function. © 2018 Society for the Experimental Analysis of Behavior.

Ada (Trade Name) Compiler Validation Summary Report. OASYS, OASYS VADS Ada Compiler, Version 1.7 InterPro 32 (NSC 32000).

DTIC Science & Technology

1986-06-19

C148008A CA3005A throueh CA3005D (14 tests) 85120011 C14A015A CE2107E BC32014C C92005A C35904A C940OACA See Appendix D for the eat descriptions. 3.5...constant NAME :a ipro sysv; STORAGE UNIT : constant :a 8; MEMORY SIZE c onstant :a 16 77 14; - System-Dependent Named N- ubers MIN INT : constant : -2

Acid-base chemistry of dissolved organic matter in aqueous leaf extracts: Application to organic acids in throughfall. [Chrysolepis sempervirens; Pinus monticola; Salix orestera

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brown, A.D.; Sposito, G.

Elemental composition data were obtained for bulk precipitation and throughfall samples and for aqueous extracts of leaves of three woody plant species common in the subalpine Sierras Nevada range, California: chinquapin (Chrysolepis sempervirens Hjelmqvist), western white pine (Pinus monticola Dougl.), and willow (Salix orestera Schneider). The acid-base equilibria of the extracts were characterized by potentiometric titration and proton formation functions were computed. The latter then were modeled assuming four classes of quasiparticle acidic functional groups, yielding negative logarithms of conditional protonation constants in the range 4.8 to 5.0, 6.1 to 6.6, 7.4 to 7.7, and 9.1 to 9.4. The relativemore » concentration of a given acidic functional group class varied markedly among the three woody species, but the conditional protonation constants were very similar. The model parameters, along with dissolved organic C concentration and pH values, were used to estimate net anion deficits in throughfall samples collected from the same sites as the leaf samples. On average, the calculated charge concentration of free organic anions in the western white pine extract matched the throughfall anion deficit, whereas the deficits in the chinquapin and willow throughfall samples were not accounted for by free anion concentrations. Metal complexation and in situ, species-dependent leaf surfaces processes may account for these latter differences.« less

The impacts of repeated cold exposure on insects.

PubMed

Marshall, Katie E; Sinclair, Brent J

2012-05-15

Insects experience repeated cold exposure (RCE) on multiple time scales in natural environments, yet the majority of studies of the effects of cold on insects involve only a single exposure. Three broad groups of experimental designs have been employed to examine the effects of RCE on insect physiology and fitness, defined by the control treatments: 'RCE vs cold', which compares RCE with constant cold conditions; 'RCE vs warm', which compares RCE with constant warm conditions; and 'RCE vs matched cold' which compares RCE with a prolonged period of cold matched by time to the RCE condition. RCE are generally beneficial to immediate survival, and increase cold hardiness relative to insects receiving a single prolonged cold exposure. However, the effects of RCE depend on the study design, and RCE vs warm studies cannot differentiate between the effects of cold exposure in general vs RCE in particular. Recent studies of gene transcription, immune function, feeding and reproductive output show that the responses of insects to RCE are distinct from the responses to single cold exposures. We suggest that future research should attempt to elucidate the mechanistic link between physiological responses and fitness parameters. We also recommend that future RCE experiments match the time spent at the stressful low temperature in all experimental groups, include age controls where appropriate, incorporate a pilot study to determine time and intensity of exposure, and measure sub-lethal impacts on fitness.

Lattice parameters and stability of the spinel compounds in relation to the ionic radii and electronegativities of constituting chemical elements.

PubMed

Brik, Mikhail G; Suchocki, Andrzej; Kamińska, Agata

2014-05-19

A thorough consideration of the relation between the lattice parameters of 185 binary and ternary spinel compounds, on one side, and ionic radii and electronegativities of the constituting ions, on the other side, allowed for establishing a simple empirical model and finding its linear equation, which links together the above-mentioned quantities. The derived equation gives good agreement between the experimental and modeled values of the lattice parameters in the considered group of spinels, with an average relative error of about 1% only. The proposed model was improved further by separate consideration of several groups of spinels, depending on the nature of the anion (oxygen, sulfur, selenium/tellurium, nitrogen). The developed approach can be efficiently used for prediction of lattice constants for new isostructural materials. In particular, the lattice constants of new hypothetic spinels ZnRE2O4, CdRE2S4, CdRE2Se4 (RE = rare earth elements) are predicted in the present Article. In addition, the upper and lower limits for the variation of the ionic radii, electronegativities, and their certain combinations were established, which can be considered as stability criteria for the spinel compounds. The findings of the present Article offer a systematic overview of the structural properties of spinels and can serve as helpful guides for synthesis of new spinel compounds.

Influence of different nominal molecular weight fractions of humic acids on phenol oxidation by permanganate.

PubMed

He, Di; Guan, Xiaohong; Ma, Jun; Yu, Min

2009-11-01

The effects of humic acid (HA) and its different nominal molecular weight (NMW) fractions on the phenol oxidation by permanganate were studied. Phenol oxidation by permanganate was enhanced by the presence of HA at pH 4-8, while slightly inhibited at pH 9-10. The effects of HA on phenol oxidation by permanganate were dependent on HA concentration and permanganate/phenol molar ratios. The high NMW fractions of HA enhanced phenol oxidation by permanganate at pH 7 more significantly than the low fractions of HA. The apparent second-order rate constants of phenol oxidation by permanganate in the presence of HA correlated well with their specific ultraviolet absorption (SUVA) at 254 nm and specific violet absorption (SVA) at 465 or 665 nm. High positive correlation coefficients (R(2) > 0.72) implied that pi-electrons of HA strongly influenced the reactivity of phenol towards permanganate oxidation which agreed well with the information provided by fluorescence spectroscopy. The FTIR analysis indicated that the HA fractions rich in aliphatic character, polysaccharide-like substances, and the amount of carboxylate groups had less effect on phenol oxidation by permanganate. The negative correlation between the rate constants of phenol oxidation by permanganate and O/C ratios suggested that the oxidation of phenol increased with a decrease in the content of oxygen-containing functional groups.

Fractional time-dependent apparent viscosity model for semisolid foodstuffs

NASA Astrophysics Data System (ADS)

Yang, Xu; Chen, Wen; Sun, HongGuang

2017-10-01

The difficulty in the description of thixotropic behaviors in semisolid foodstuffs is the time dependent nature of apparent viscosity under constant shear rate. In this study, we propose a novel theoretical model via fractional derivative to address the high demand by industries. The present model adopts the critical parameter of fractional derivative order α to describe the corresponding time-dependent thixotropic behavior. More interestingly, the parameter α provides a quantitative insight into discriminating foodstuffs. With the re-exploration of three groups of experimental data (tehineh, balangu, and natillas), the proposed methodology is validated in good applicability and efficiency. The results show that the present fractional apparent viscosity model performs successfully for tested foodstuffs in the shear rate range of 50-150 s^{ - 1}. The fractional order α decreases with the increase of temperature at low temperature, below 50 °C, but increases with growing shear rate. While the ideal initial viscosity k decreases with the increase of temperature, shear rate, and ingredient content. It is observed that the magnitude of α is capable of characterizing the thixotropy of semisolid foodstuffs.

The Effect of Variability of Practice at Execution Redundancy Level in Skilled and Novice Basketball Players.

PubMed

Taheri, Hamidreza; Fazeli, Davoud; Poureghbali, Sogand

2017-04-01

We investigated the effect of practice variability through execution redundancy in skilled and novice basketball players on free throw skills. Twelve skilled basketball players and 12 novices (mean age = 25.4 years, SD = 4.3) were divided into four groups (skilled constant, skilled variable, novice constant, and novice variable). After a pretest, participants practiced free throw action. The variable groups threw the ball over an obstacle of varying heights on each trial in random order, whereas the obstacle's height was fixed for the constant groups. After 7 and 14 consecutive days of practice, participants performed two posttests with constant and variable distances from the basket. The results showed that practicing different solutions of a task did not affect the performance of skilled players but had an immediate negative effect on the performance of novice players. Learning a complex task is the result of learning task-related parameters, and practice variability can create a mismatch between task difficulty and new learner skill levels.

Infrared dielectric functions and optical phonons of wurtzite Y x Al1-x N (0  ⩽  x  ⩽  0.22)

NASA Astrophysics Data System (ADS)

Ben Sedrine, N.; Zukauskaite, A.; Birch, J.; Jensen, J.; Hultman, L.; Schöche, S.; Schubert, M.; Darakchieva, V.

2015-10-01

YAlN is a new member of the group-III nitride family with potential for applications in next generation piezoelectric and light emitting devices. We report the infrared dielectric functions and optical phonons of wurtzite (0001) Y x Al1-x N epitaxial films with 0  ⩽  x  ⩽  0.22. The films are grown by magnetron sputtering epitaxy on c-plane Al2O3 and their phonon properties are investigated using infrared spectroscopic ellipsometry and Raman scattering spectroscopy. The infrared-active E 1(TO) and LO, and the Raman active E 2 phonons are found to exhibit one-mode behavior, which is discussed in the framework of the MREI model. The compositional dependencies of the E 1(TO), E 2 and LO phonon frequencies, the high-frequency limit of the dielectric constant, {{\\varepsilon}∞} , the static dielectric constant, {{\\varepsilon}0} , and the Born effective charge Z B are established and discussed.

First-Principles pH Theory

NASA Astrophysics Data System (ADS)

Kim, Yong-Hyun; Zhang, S. B.

2006-03-01

Despite being one of the most important macroscopic measures and a long history even before the quantum mechanics, the concept of pH has rarely been mentioned in microscopic theories, nor being incorporated computationally into first-principles theory of aqueous solutions. Here, we formulate a theory for the pH dependence of solution formation energy by introducing the proton chemical potential as the microscopic counterpart of pH in atomistic solution models. Within the theory, the general acid-base chemistry can be cast in a simple pictorial representation. We adopt density-functional molecular dynamics to demonstrate the usefulness of the method by studying a number of solution systems including water, small solute molecules such as NH3 and HCOOH, and more complex amino acids with several functional groups. For pure water, we calculated the auto- ionization constant to be 13.2 with a 95 % accuracy. For other solutes, the calculated dissociation constants, i.e., the so- called pKa, are also in reasonable agreement with experiments. Our first-principles pH theory can be readily applied to broad solution chemistry problems such as redox reactions.

Electrostatic correlations at the Stern layer: Physics or chemistry?

NASA Astrophysics Data System (ADS)

Travesset, A.; Vangaveti, S.

2009-11-01

We introduce a minimal free energy describing the interaction of charged groups and counterions including both classical electrostatic and specific interactions. The predictions of the model are compared against the standard model for describing ions next to charged interfaces, consisting of Poisson-Boltzmann theory with additional constants describing ion binding, which are specific to the counterion and the interfacial charge ("chemical binding"). It is shown that the "chemical" model can be appropriately described by an underlying "physical" model over several decades in concentration, but the extracted binding constants are not uniquely defined, as they differ depending on the particular observable quantity being studied. It is also shown that electrostatic correlations for divalent (or higher valence) ions enhance the surface charge by increasing deprotonation, an effect not properly accounted within chemical models. The charged phospholipid phosphatidylserine is analyzed as a concrete example with good agreement with experimental results. We conclude with a detailed discussion on the limitations of chemical or physical models for describing the rich phenomenology of charged interfaces in aqueous media and its relevance to different systems with a particular emphasis on phospholipids.

Studies on structural, electrical, thermal and magnetic properties of YFeO3 ceramic

NASA Astrophysics Data System (ADS)

Suthar, Lokesh; Jha, V. K.; Bhadala, Falguni; Roy, M.; Sahu, S.; Barbar, S. K.

2017-10-01

The polycrystalline ceramic sample of YFeO3 has been synthesized by high-temperature solid-state reaction method using high-purity oxides. The formation of the compound has been confirmed by the room temperature (RT) X-ray diffraction analysis. The refined lattice parameters obtained by Rietveld analysis are: a = 5.5907 Å, b = 7.6082 Å and c = 5.2849 Å with orthorhombic symmetry in space group Pnma. The average grain size obtained from the SEM micrograph is around 2 µm. The three-dimensional surface morphology has been investigated using atomic force microscopy (AFM), and the average roughness measured in the sampling area of 100.07 µm2 is around 142 nm. The frequency- and temperature-dependent dielectric constant has been measured. The material shows high dielectric constant value (750) at RT. The activation energy obtained from dc conductivity using Arrhenius relation σ = σ oexp(-Ea/kT) is 2.12 eV. Thermal analysis shows phase change around 625 K with minimum weight loss (i.e. 1.27% of initial weight) from RT to 1273 K. The magnetization measurement indicates soft magnetic behaviour.

Organic solar cells based on high dielectric constant materials: An approach to increase efficiency

NASA Astrophysics Data System (ADS)

Hamam, Khalil Jumah Tawfiq

The efficiency of organic solar cells still lags behind inorganic solar cells due to their low dielectric constant which results in a weakly screened columbic attraction between the photogenerated electron-hole system, therefore the probability of charge separating is low. Having an organic material with a high dielectric constant could be the solution to get separated charges or at least weakly bounded electron-hole pairs. Therefore, high dielectric constant materials have been investigated and studied by measuring modified metal-phthalocyanine (MePc) and polyaniline in pellets and thin films. The dielectric constant was investigated as a function of temperature and frequency in the range of 20Hz to1MHz. For MePc we found that the high dielectric constant was an extrinsic property due to water absorption and the formation of hydronuim ion allowed by the ionization of the functional groups such as sulphonated and carboxylic groups. The dielectric constant was high at low frequencies and decreasing as the frequency increase. Investigated materials were applied in fabricated bilayer heterojunction organic solar cells. The application of these materials in an organic solar cells show a significant stability under room conditions rather than improvement in their efficiency.

Experimental Programs and Programmatic Experiments.

ERIC Educational Resources Information Center

Kent, Robert

When assembling or evaluating experimental programs in college English, the crucial fact to be remembered is that the success of the undertaking depends more on the teachers than on the program itself, for it is men, not programs, who fail in the constant experiment with books. Teachers need to be adventurous, constantly rereading, rethinking, and…

Enzymatic mechanisms of biological magnetic sensitivity.

PubMed

Letuta, Ulyana G; Berdinskiy, Vitaly L; Udagawa, Chikako; Tanimoto, Yoshifumi

2017-10-01

Primary biological magnetoreceptors in living organisms is one of the main research problems in magnetobiology. Intracellular enzymatic reactions accompanied by electron transfer have been shown to be receptors of magnetic fields, and spin-dependent ion-radical processes can be a universal mechanism of biological magnetosensitivity. Magnetic interactions in intermediate ion-radical pairs, such as Zeeman and hyperfine (HFI) interactions, in accordance with proposed strict quantum mechanical theory, can determine magnetic-field dependencies of reactions that produce biologically important molecules needed for cell growth. Hyperfine interactions of electrons with nuclear magnetic moments of magnetic isotopes can explain the most important part of biomagnetic sensitivities in a weak magnetic field comparable to the Earth's magnetic field. The theoretical results mean that magnetic-field dependencies of enzymatic reaction rates in a weak magnetic field that can be independent of HFI constant a, if H < a, and are determined by the rate constant of chemical transformations in the enzyme active site. Both Zeeman and HFI interactions predict strong magnetic-field dependence in weak magnetic fields and magnetic-field independence of enzymatic reaction rate constants in strong magnetic fields. The theoretical results can explain the magnetic sensitivity of E. coli cell and demonstrate that intracellular enzymatic reactions are primary magnetoreceptors in living organisms. Bioelectromagnetics. 38:511-521, 2017. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Blue-enriched office light competes with natural light as a zeitgeber.

PubMed

Vetter, Céline; Juda, Myriam; Lang, Dieter; Wojtysiak, Andreas; Roenneberg, Till

2011-09-01

Circadian regulation of human physiology and behavior (eg, body temperature or sleep-timing), depends on the "zeitgeber" light that synchronizes them to the 24-hour day. This study investigated the effect of changing light temperature at the workplace from 4000 Kelvin (K) to 8000 K on sleep-wake and activity-rest behavior. An experimental group (N=27) that experienced the light change was compared with a non-intervention group (N=27) that remained in the 4000 K environment throughout the 5-week study period (14 January to 17 February). Sleep logs and actimetry continuously assessed sleep-wake behavior and activity patterns. Over the study period, the timing of sleep and activity on free days steadily advanced parallel to the seasonal progression of sunrise in the non-intervention group. In contrast, the temporal pattern of sleep and activity in the experimental group remained associated with the constant onset of work. The results suggest that artificial blue-enriched light competes with natural light as a zeitgeber. While subjects working under the warmer light (4000 K) appear to entrain (or synchronize) to natural dawn, the subjects who were exposed to blue-enriched (8000 K) light appear to entrain to office hours. The results confirm that light is the dominant zeitgeber for the human clock and that its efficacy depends on spectral composition. The results also indicate that blue-enriched artificial light is a potent zeitgeber that has to be used with diligence.

Adsorption of surfactant ions and binding of their counterions at an air/water interface.

PubMed

Tagashira, Hiroaki; Takata, Youichi; Hyono, Atsushi; Ohshima, Hiroyuki

2009-01-01

An expression for the surface tension of an aqueous mixed solution of surfactants and electrolyte ions in the presence of the common ions was derived from the Helmholtz free energy of an air/water surface. By applying the equation to experimental data for the surface tension, the adsorption constant of surfactant ions onto the air/water interface, the binding constant of counterions on the surfactants, and the surface potential and surface charge density of the interface were estimated. The adsorption constant and binding constant were dependent on the species of surfactant ion and counterion, respectively. Taking account of the dependence of surface potential and surface charge density on the concentration of electrolyte, it was suggested that the addition of electrolyte to the aqueous surfactant solution brings about the decrease in the surface potential, the increase in the surface density of surfactant ions, and consequently, the decrease in the surface tension. Furthermore, it was found that the configurational entropy plays a predominant role for the surface tension, compared to the electrical work.

The varying cosmological constant: a new approximation to the Friedmann equations and universe model

NASA Astrophysics Data System (ADS)

Öztaş, Ahmet M.; Dil, Emre; Smith, Michael L.

2018-05-01

We investigate the time-dependent nature of the cosmological constant, Λ, of the Einstein Field Equation (EFE). Beginning with the Einstein-Hilbert action as our fundamental principle we develop a modified version of the EFE allowing the value of Λ to vary as a function of time, Λ(t), indirectly, for an expanding universe. We follow the evolving Λ presuming four-dimensional space-time and a flat universe geometry and present derivations of Λ(t) as functions of the Hubble constant, matter density, and volume changes which can be traced back to the radiation epoch. The models are more detailed descriptions of the Λ dependence on cosmological factors than previous, allowing calculations of the important parameters, Ωm and Ωr, to deep lookback times. Since we derive these without the need for extra dimensions or other special conditions our derivations are useful for model evaluation with astronomical data. This should aid resolution of several difficult problems of astronomy such as the best value for the Hubble constant at present and at recombination.

New 1,6-heptadienes with pyrimidine bases attached: Syntheses and spectroscopic analyses

NASA Astrophysics Data System (ADS)

Hammud, Hassan H.; Ghannoum, Amer M.; Fares, Fares A.; Abramian, Lara K.; Bouhadir, Kamal H.

2008-06-01

A simple, high yielding synthesis leading to the functionalization of some pyrimidine bases with a 1,6-heptadienyl moiety spaced from the N - 1 position by a methylene group is described. A key step in this synthesis involves a Mitsunobu reaction by coupling 3N-benzoyluracil and 3N-benzoylthymine to 2-allyl-pent-4-en-1-ol followed by alkaline hydrolysis of the 3N-benzoyl protecting groups. This protocol should eventually lend itself to the synthesis of a host of N-alkylated nucleoside analogs. The absorption and emission properties of these pyrimidine derivatives ( 3- 6) were studied in solvents of different physical properties. Computerized analysis and multiple regression techniques were applied to calculate the regression and correlation coefficients based on the equation that relates peak position λmax to the solvent parameters that depend on the H-bonding ability, refractive index, and dielectric constant of solvents.

Plasma parameters in a multidipole plasma system

NASA Astrophysics Data System (ADS)

Ruscanu, D.; Anita, V.; Popa, G.

Plasma potential and electron number densities and electron temperatures under bi-Maxwellian approximation for electron distribution function of the multidipole argon plasma source system were measured for a gas pressure ranging between 10-4 and 10-3 mbar and an anode-cathode voltage ranging between 40 and 120 V but a constant discharge current intensity. The first group, as ultimate or cold electrons and main electron plasma population, results by trapping of the slow electrons produced by ionisation process due to primary-neutral collisions. The trapping process is produced by potential well due to positive plasma potential with respect to the anode so that electron temperature of the ultimate electrons does not depend on both the gas pressure and discharge voltage. The second group, as secondary or hot electrons, results as degrading process of the primaries and their number density increases while their temperature decreases with the increase of both the gas pressure and discharge voltage.

Force field refinement from NMR scalar couplings

NASA Astrophysics Data System (ADS)

Huang, Jing; Meuwly, Markus

2012-03-01

NMR observables contain valuable information about the protein dynamics sampling a high-dimensional potential energy surface. Depending on the observable, the dynamics is sensitive to different time-windows. Scalar coupling constants hJ reflect the pico- to nanosecond motions associated with the intermolecular hydrogen bond network. Including an explicit H-bond in the molecular mechanics with proton transfer (MMPT) potential allows us to reproduce experimentally determined hJ couplings to within 0.02 Hz at best for ubiquitin and protein G. This is based on taking account of the chemically changing environment by grouping the H-bonds into up to seven classes. However, grouping them into two classes already reduces the RMSD between computed and observed hJ couplings by almost 50%. Thus, using ensemble-averaged data with two classes of H-bonds leads to substantially improved scalar couplings from simulations with accurate force fields.

On the possibility of negative activation energies in bimolecular reactions

NASA Technical Reports Server (NTRS)

Jaffe, R. L.

1978-01-01

The temperature dependence of the rate constants for model reacting systems was studied to understand some recent experimental measurements which imply the existence of negative activation energies. A collision theory model and classical trajectory calculations are used to demonstrate that the reaction probability can vary inversely with collision energy for bimolecular reactions occurring on attractive potential energy surfaces. However, this is not a sufficient condition to ensure that the rate constant has a negative temperature dependence. On the basis of these calculations, it seems unlikely that a true bimolecular reaction between neutral molecules will have a negative activation energy.

Dielectric properties of CaCu3Ti4O12-silicone resin composites

NASA Astrophysics Data System (ADS)

Babu, Sanjesh; Singh, Kirti; Govindan, Anil

2012-06-01

CaCu3Ti4O12 (CCTO)-silicone resin composites with various CCTO volume fractions were prepared. Relatively high dielectric constant ( ɛ=119) and low loss (tan δ=0.35) of the composites with CCTO volume fraction of 0.9 were observed. Two theoretical models were employed to predict the dielectric constant of these composites; the dielectric constant obtained via the Maxwell-Garnett model was in close agreement with the experimental data. The dielectric constant of CCTO-silicone resin composites showed a weak frequency dependence at the measuring frequency range and the loss tangent apparently decreases with increase in frequency.

Predicting elastic properties of β-HMX from first-principles calculations.

PubMed

Peng, Qing; Rahul; Wang, Guangyu; Liu, Gui-Rong; Grimme, Stefan; De, Suvranu

2015-05-07

We investigate the performance of van der Waals (vdW) functions in predicting the elastic constants of β cyclotetramethylene tetranitramine (HMX) energetic molecular crystals using density functional theory (DFT) calculations. We confirm that the accuracy of the elastic constants is significantly improved using the vdW corrections with environment-dependent C6 together with PBE and revised PBE exchange-correlation functionals. The elastic constants obtained using PBE-D3(0) calculations yield the most accurate mechanical response of β-HMX when compared with experimental stress-strain data. Our results suggest that PBE-D3 calculations are reliable in predicting the elastic constants of this material.

Solvent Dependence of Double Proton Transfer in the Formic Acid-Formamidine Complex: Path Integral Molecular Dynamics Investigation.

PubMed

Kungwan, Nawee; Ngaojampa, Chanisorn; Ogata, Yudai; Kawatsu, Tsutomu; Oba, Yuki; Kawashima, Yukio; Tachikawa, Masanori

2017-10-05

Solvent dependence of double proton transfer in the formic acid-formamidine (FA-FN) complex at room temperature was investigated by means of ab initio path integral molecular dynamics (AIPIMD) simulation with taking nuclear quantum and thermal effects into account. The conductor-like screening model (COSMO) was applied for solvent effect. In comparison with gas phase, double proton delocalization between two heavy atoms (O and N) in FA-FN were observed with reduced proton transfer barrier height in low dielectric constant medium (<4.8). For dielectric constant medium at 4.8, the chance of finding these two protons are more pronounced due to the solvent effect which completely washes out the proton transfer barrier. In the case of higher dielectric constant medium (>4.8), the ionic species becomes more stable than the neutral ones and the formate anion and formamidium cation are thermodynamically stable. For ab initio molecular dynamics simulation, in low dielectric constant medium (<4.8) a reduction of proton transfer barrier with solvent effect is found to be less pronounced than the AIPIMD due to the absence of nuclear quantum effect. Moreover, the motions of FA-FN complex are significantly different with increasing dielectric constant medium. Such a difference is revealed in detail by the principal component analysis.

Vacuum phase transition solves the H0 tension

NASA Astrophysics Data System (ADS)

Di Valentino, Eleonora; Linder, Eric V.; Melchiorri, Alessandro

2018-02-01

Taking the Planck cosmic microwave background data and the more direct Hubble constant measurement data as unaffected by systematic offsets, the values of the Hubble constant H0 interpreted within the Λ CDM cosmological constant and cold dark matter cosmological model are in ˜3.3 σ tension. We show that the Parker vacuum metamorphosis (VM) model, physically motivated by quantum gravitational effects and with the same number of parameters as Λ CDM , can remove the H0 tension and can give an improved fit to data (up to a mean Δ χ2=-7.5 ). It also ameliorates tensions with weak lensing data and the high redshift Lyman alpha forest data. Considering Bayesian evidence, we found in the case of the Planck data set alone positive evidence for a VM model against a cosmological constant both in the six- and nine-parameter framework. When the R16 data set is also considered, we found a strong evidence for the VM model against a cosmological constant in nine-parameter space. We separately consider a scale-dependent scaling of the gravitational lensing amplitude, such as provided by modified gravity, neutrino mass, or cold dark energy, motivated by the somewhat different cosmological parameter estimates for low and high CMB multipoles. We find that no such scale dependence is preferred.

Correlations between the disintegration of melt and the measured impulses in steam explosions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Froehlich, G.; Linca, A.; Schindler, M.

To find our correlations in steam explosions (melt water interactions) between the measured impulses and the disintegration of the melt, experiments were performed in three configurations i.e. stratified, entrapment and jet experiments. Linear correlations were detected between the impulse and the total surface of the fragments. Theoretical considerations point out that a linear correlation assumes superheating of a water layer around the fragments of a constant thickness during the fragmentation process to a constant temperature (here the homogeneous nucleation temperature of water was assumed) and a constant expansion velocity of the steam in the main expansion time. The correlation constantmore » does not depend on melt temperature and trigger pressure, but it depends on the configuration of the experiment or of a scenario of an accident. Further research is required concerning the correlation constant. For analysing steam explosion accidents the explosivity is introduced. The explosivity is a mass specific impulse. The explosivity is linear correlated with the degree of fragmentation. Knowing the degree of fragmentation with proper correlation constant the explosivity can be calculated and from the explosivity combined with the total mass of fragments the impulse is obtained which can be used to an estimation of the maximum force.« less

Dielectric and impedance spectral characteristics of bulk ZnIn2Se4

NASA Astrophysics Data System (ADS)

El-Nahass, M. M.; Attia, A. A.; Salem, G. F.; Ali, H. A. M.; Ismail, M. I.

2014-02-01

The frequency and temperature dependence of ac conductivity, dielectric constant and dielectric loss of ZnIn2Se4 in a pellet form were investigated in the frequency range of 102-106 Hz and temperature range of 293-356 K. The behavior of ac conductivity was interpreted by the correlated barrier hopping (CBH) model. Temperature dependence of ac conductivity indicates that ac conduction is a thermally activated process. The density of localized states N(EF) and ac activation energy were estimated for various frequencies. Dielectric constant and dielectric loss showed a decrease with increasing frequency and an increase with increasing in temperature. The frequency dependence of real and imaginary parts of the complex impedance was investigated. The relaxation time decreases with the increase in temperature. The impedance spectrum exhibits the appearance of the single semicircular arc. The radius of semicircular arcs decreases with increasing temperature which suggests a mechanism of temperature-dependent on relaxation.

Wavelength dependent in-plane birefringence of transparent flexible films determined by using transmission ellipsometry

NASA Astrophysics Data System (ADS)

Yang, Sung Mo; Hong, Sera; Kim, Sang Youl

2018-05-01

We introduce a simple method to determine the in-plane birefringence of transparent flexible films by using transmission spectroscopic ellipsometry. The pseudo-ellipsometric constants which can represent their sample azimuthal angle dependent characteristics are introduced. The effect of in-plane birefringence and sample azimuthal angle on the pseudo ellipsometric constants is calculated using Jones matrix formalism, and the observed sample azimuthal angle dependence of measured pseudo-ellipsometric data is well understood. Wavelength dependence of in-plane birefringence is expressed in terms of the Sellmeier dispersion equation. The best fit pseudo-ellipsometric spectra to the measured ones at the sample azimuthal angles of every 15° from 0 to 90° are searched. The dispersion coefficients of the Sellmeier equation and the azimuthal angle of the optic axis are determined for polycarbonate (PC), poly(ethylene naphthalate) (PEN), poly(ethylene terephthalate) (PET), polyimide (PI), and colorless polyimide (CPI) films.

Influence of tantalum underlayer on magnetization dynamics in Ni{sub 81}Fe{sub 19} films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kwon, Jae Hyun; Deorani, Praveen; Yoon, Jungbum

2015-07-13

The effect of tantalum (Ta) underlayer is investigated in Ni{sub 81}Fe{sub 19} thin films for magnetization dynamics. The damping parameters extracted from spin wave measurements increase systematically with increasing Ta thickness, whereas the damping parameters from ferromagnetic resonance measurements are found to be weakly dependent on the Ta thickness. The difference is attributed to propagating properties of spin wave and short spin diffusion length in Ta. The group velocity of spin waves is found to be constant for different Ta thicknesses, and nonreciprocity of spin waves is not affected by the Ta thickness. The experimental observations are supported by micromagneticmore » simulations.« less

Cosmological constant and quantum gravitational corrections to the running fine structure constant.

PubMed

Toms, David J

2008-09-26

The quantum gravitational contribution to the renormalization group behavior of the electric charge in Einstein-Maxwell theory with a cosmological constant is considered. Quantum gravity is shown to lead to a contribution to the running charge not present when the cosmological constant vanishes. This reopens the possibility, suggested by Robinson and Wilczek, of altering the scaling behavior of gauge theories at high energies although our result differs. We show the possibility of an ultraviolet fixed point that is linked directly to the cosmological constant.

Just noticeable differences of open quotient and asymmetry coefficient in singing voice.

PubMed

Henrich, Nathalie; Sundin, Gunilla; Ambroise, Daniel; d'Alessandro, Christophe; Castellengo, Michèle; Doval, Boris

2003-12-01

This study aims to explore the perceptual relevance of the variations of glottal flow parameters and to what extent a small variation can be detected. Just Noticeable Differences (JNDs) have been measured for three values of open quotient (0.4, 0.6, and 0.8) and two values of asymmetry coefficient (2/3 and 0.8), and the effect of changes of vowel, pitch, vibrato, and amplitude parameters has been tested. Two main groups of subjects have been analyzed: a group of 20 untrained subjects and a group of 10 trained subjects. The results show that the JND for open quotient is highly dependent on the target value: an increase of the JND is noticed when the open quotient target value is increased. The relative JND is constant: deltaOq/Oq = 14% for the untrained and 10% for the trained. In the same way, the JND for asymmetry coefficient is also slightly dependent on the target value--an increase of the asymmetry coefficient value leads to a decrease of the JND. The results show that there is no effect from the selected vowel or frequency (two values have been tested), but that the addition of a vibrato has a small effect on the JND of open quotient. The choice of an amplitude parameter also has a great effect on the JND of open quotient.

Dose-dependent establishment of Trichuris suis larvae in Göttingen minipigs.

PubMed

Vejzagić, Nermina; Roepstorff, Allan; Kringel, Helene; Thamsborg, Stig Milan; Nielsen, Mads Pårup; Kapel, Christian M O

2015-03-15

Embryonated eggs of the pig whipworm Trichuris suis (TSOee) constitute the active pharmaceutical ingredient (API) in a medicinal product explored in human clinical trials against several immune-mediated diseases. The measurement of TSO biological potency (hatchability and infectivity) is a requirement for the assessment of TSO's pharmacological potency in human clinical trials. The present study aims to validate the dose-dependent establishment of T. suis larvae in Göttingen minipigs and eventual clinical implication of a dose range (1000-10,000 TSO). Four groups of 5 minipigs were inoculated with doses of 1000, 2500, 7500, and 10,000 TSOee, respectively, to evaluate a range of concentrations of TSOee in a minipig infectivity model. Unembryonated eggs (TSOue) were added to keep the total egg number in the inoculum constant at 10,000 eggs. Two groups received 2500 and 7500 TSOee per pig without the addition of TSOue as controls. The intestinal larval establishment at 21 days post inoculation (dpi) demonstrated a clear positive linear dose-response relationship between numbers of inoculated TSOee and recovered larvae. There was a low level of variation in larval counts in all study groups. Thus, the infectivity model in minipigs within the tested dose range offers a reliable, sensitive and accurate assay for testing biological potency of TSO. Copyright © 2015 Elsevier B.V. All rights reserved.

Andrographolide sodium bisulphite-induced inactivation of urease: inhibitory potency, kinetics and mechanism.

PubMed

Mo, Zhi-Zhun; Wang, Xiu-Fen; Zhang, Xie; Su, Ji-Yan; Chen, Hai-Ming; Liu, Yu-Hong; Zhang, Zhen-Biao; Xie, Jian-Hui; Su, Zi-Ren

2015-07-16

The inhibitory effect of andrographolide sodium bisulphite (ASB) on jack bean urease (JBU) and Helicobacter pylori urease (HPU) was performed to elucidate the inhibitory potency, kinetics and mechanism of inhibition in 20 mM phosphate buffer, pH 7.0, 2 mM EDTA, 25 °C. The ammonia formations, indicator of urease activity, were examined using modified spectrophotometric Berthelot (phenol-hypochlorite) method. The inhibitory effect of ASB was characterized with IC50 values. Lineweaver-Burk and Dixon plots for JBU inhibition of ASB was constructed from the kinetic data. SH-blocking reagents and competitive active site Ni2+ binding inhibitors were employed for mechanism study. Molecular docking technique was used to provide some information on binding conformations as well as confirm the inhibition mode. The IC50 of ASB against JBU and HPU was 3.28±0.13 mM and 3.17±0.34 mM, respectively. The inhibition proved to be competitive and concentration- dependent in a slow-binding progress. The rapid formation of initial ASB-JBU complex with an inhibition constant of Ki=2.86×10(-3) mM was followed by a slow isomerization into the final complex with an overall inhibition constant of Ki*=1.33×10(-4) mM. The protective experiment proved that the urease active site is involved in the binding of ASB. Thiol reagents (L-cysteine and dithiothreithol) strongly protect the enzyme from the loss of enzymatic activity, while boric acid and fluoride show weaker protection, indicating that the active-site sulfhydryl group of JBU was potentially involved in the blocking process. Moreover, inhibition of ASB proved to be reversible since ASB-inactivated JBU could be reactivated by dithiothreitol application. Molecular docking assay suggested that ASB made contacts with the important sulfhydryl group Cys-592 residue and restricted the mobility of the active-site flap. ASB was a competitive inhibitor targeting thiol groups of urease in a slow-binding manner both reversibly and concentration-dependently, serving as a promising urease inhibitor for the treatment of urease-related diseases.

Theoretical spectroscopic characterization at low temperatures of detectable sulfur-organic compounds: Ethyl mercaptan and dimethyl sulfide

NASA Astrophysics Data System (ADS)

Senent, M. L.; Puzzarini, C.; Domínguez-Gómez, R.; Carvajal, M.; Hochlaf, M.

2014-03-01

Highly correlated ab initio methods are used for the spectroscopic characterization of ethyl mercaptan (CH3CH232SH, ETSH) and dimethyl sulfide (CH332SCH3, DMS), considering them on the vibrational ground and excited torsional states. Since both molecules show non-rigid properties, torsional energy barriers and splittings are provided. Equilibrium geometries and the corresponding rotational constants are calculated by means of a composite scheme based on CCSD(T) calculations that accounts for the extrapolation to the complete basis set limit and core-correlation effects. The ground and excited states rotational constants are then determined using vibrational corrections obtained from CCSD/cc-pVTZ force-field calculations, which are also employed to determine anharmonic frequencies for all vibrational modes. CCSD(T) and CCSD force fields are employed to predict quartic and sextic centrifugal-distortion constants, respectively. Equilibrium rotational constants are also calculated using CCSD(T)-F12. The full-dimensional anharmonic analysis does not predict displacements of the lowest torsional excited states due to Fermi resonances with the remaining vibrational modes. Thus, very accurate torsional transitions are calculated by solving variationally two-dimensional Hamiltonians depending on the CH3 and SH torsional coordinates of ethyl mercaptan or on the two methyl groups torsions of dimethyl-sulfide. For this purpose, vibrationally corrected potential energy surfaces are computed at the CCSD(T)/aug-cc-pVTZ level of theory. For ethyl mercaptan, calculations show large differences between the gauche (g) and trans (t) conformer spectral features. Interactions between rotating groups are responsible for the displacements of the g-bands with respect to the t-bands that cannot therefore be described with one-dimensional models. For DMS, the CCSD(T) potential energy surface has been semi-empirically adjusted to reproduce experimental data. New assignments are suggested for the methyl torsion bands of ETSH and a reassignment is proposed for the infrared bands of DMS (0 3 → 0 4 and 1 0 → 1 1). Our accurate spectroscopic data should be useful for the analysis of the microwave and far infrared spectra of ETSH and DMS recorded, at low temperatures, either in laboratory or in the interstellar medium.

Ion transport with charge-protected and non-charge-protected cations in alcohol-based electrolytes using the compensated Arrhenius formalism. Part I: ionic conductivity and the static dielectric constant.

PubMed

Petrowsky, Matt; Fleshman, Allison; Frech, Roger

2012-05-17

The temperature dependence of ionic conductivity and the static dielectric constant is examined for 0.30 m TbaTf- or LiTf-1-alcohol solutions. Above ambient temperature, the conductivity increases with temperature to a greater extent in electrolytes whose salt has a charge-protected cation. Below ambient temperature, the dielectric constant changes only slightly with temperature in electrolytes whose salt has a cation that is not charge-protected. The compensated Arrhenius formalism is used to describe the temperature-dependent conductivity in terms of the contributions from both the exponential prefactor σo and Boltzmann factor exp(-Ea/RT). This analysis explains why the conductivity decreases with increasing temperature above 65 °C for the LiTf-dodecanol electrolyte. At higher temperatures, the decrease in the exponential prefactor is greater than the increase in the Boltzmann factor.

The Pressure Dependence of Structural, Electronic, Mechanical, Vibrational, and Thermodynamic Properties of Palladium-Based Heusler Alloys

NASA Astrophysics Data System (ADS)

Çoban, Cansu

2017-08-01

The pressure dependent behaviour of the structural, electronic, mechanical, vibrational, and thermodynamic properties of Pd2TiX (X=Ga, In) Heusler alloys was investigated by ab initio calculations. The lattice constant, the bulk modulus and its first pressure derivative, the electronic band structure and the density of states (DOS), mechanical properties such as elastic constants, anisotropy factor, Young's modulus, etc., the phonon dispersion curves and phonon DOS, entropy, heat capacity, and free energy were obtained under pressure. It was determined that the calculated lattice parameters are in good agreement with the literature, the elastic constants obey the stability criterion, and the phonon dispersion curves have no negative frequency which shows that the compounds are stable. The band structures at 0, 50, and 70 GPa showed valence instability at the L point which explains the superconductivity in Pd2TiX (X=Ga, In).

Aggregate linear properties of ferroelectric ceramics and polycrystalline thin films: Calculation by the method of effective piezoelectric medium

NASA Astrophysics Data System (ADS)

Pertsev, N. A.; Zembilgotov, A. G.; Waser, R.

1998-08-01

The effective dielectric, piezoelectric, and elastic constants of polycrystalline ferroelectric materials are calculated from single-crystal data by an advanced method of effective medium, which takes into account the piezoelectric interactions between grains in full measure. For bulk BaTiO3 and PbTiO3 polarized ceramics, the dependences of material constants on the remanent polarization are reported. Dielectric and elastic constants are computed also for unpolarized c- and a-textured ferroelectric thin films deposited on cubic or amorphous substrates. It is found that the dielectric properties of BaTiO3 and PbTiO3 polycrystalline thin films strongly depend on the type of crystal texture. The influence of two-dimensional clamping by the substrate on the dielectric and piezoelectric responses of polarized films is described quantitatively and shown to be especially important for the piezoelectric charge coefficient of BaTiO3 films.

Adiabatic Coupling Constant of Nitrobenzene- n-Alkane Critical Mixtures. Evidence from Ultrasonic Spectra and Thermodynamic Data

NASA Astrophysics Data System (ADS)

Mirzaev, Sirojiddin Z.; Kaatze, Udo

2016-09-01

Ultrasonic spectra of mixtures of nitrobenzene with n-alkanes, from n-hexane to n-nonane, are analyzed. They feature up to two Debye-type relaxation terms with discrete relaxation times and, near the critical point, an additional relaxation term due to the fluctuations in the local concentration. The latter can be well represented by the dynamic scaling theory. Its amplitude parameter reveals the adiabatic coupling constant of the mixtures of critical composition. The dependence of this thermodynamic parameter upon the length of the n-alkanes corresponds to that of the slope in the pressure dependence of the critical temperature and is thus taken another confirmation of the dynamic scaling model. The change in the variation of the coupling constant and of several other mixture parameters with alkane length probably reflects a structural change in the nitrobenzene- n-alkane mixtures when the number of carbon atoms per alkane exceeds eight.

Core-shell structured polystyrene/BaTiO3 hybrid nanodielectrics prepared by in situ RAFT polymerization: a route to high dielectric constant and low loss materials with weak frequency dependence.

PubMed

Yang, Ke; Huang, Xingyi; Xie, Liyuan; Wu, Chao; Jiang, Pingkai; Tanaka, Toshikatsu

2012-11-23

A novel route to prepare core-shell structured nanocomposites with excellent dielectric performance is reported. This approach involves the grafting of polystyrene (PS) from the surface of BaTiO(3) by an in situ RAFT polymerization. The core-shell structured PS/BaTiO(3) nanocomposites not only show significantly increased dielectric constant and very low dielectric loss, but also have a weak frequency dependence of dielectric properties over a wide range of frequencies. In addition, the dielectric constant of the nanocomposites can also be easily tuned by varying the thickness of the PS shell. Our method is very promising for preparing high-performance nanocomposites used in energy-storage devices. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DIFF--A 7090 Fortran Program to Determine Neutron Diffusion Constants Relating to a Six-Group Calculation; DIFF--UN PROGRAMME FOR TRAN 7090 POUR DETERMINER LES CONSTANTES DE DIFFUSION NEUTRONIQUE RELATIVES A UN CALCUL A SIX GROUPES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Plelnevaux, C.

The computer program DIFF, in Fortran for the IBM 7090, for calculating the neutron diffusion coefficients and attenuation areas (L/sup 2/) necessary for multigroup diffusion calculations for reactor shielding is described. Diffusion coefficients and values of the inverse attenuation length are given for a six group calculation for several interesting shielding materials. (D.C.W.)

Histological Evaluation of Nano-Micro Titanium Implant Surface Treatment in Beagle Humerus.

PubMed

Yun, Kwidug; Kang, Seongsoo; Oh, Gyejeong; Lim, Hyunpil; Lee, Kwangmin; Yang, Hongso; Vang, Mongsook; Park, Sangwon

2016-02-01

The objective of this study was to investigate the effects of nano-micro titanium implant surface using histology in beagle dogs. A total of 48 screw-shaped implants (Megagen, Daegu, Korea) which dimensions were 4 mm in diameter and 8.5 mm in length, were used. The implants were classified into 4 groups (n = 12): machined surface (M group), RBM (Resorbable Blasting Media) surface (R group), nano surface which is nanotube formation on the machined surface (MA group) and nano-micro surface which is nanotube formation on the RBM surface (RA group). Anodic oxidation was performed at a constant voltage of 20 V for 10 min using a DC power supply (Fine Power F-3005; SG EMD, Anyang, Korea). The bone blocks were investigated using histology. There was no inflammation around implants, and new bone formation was shown along with the nano-micro titanium implant surfaces. The amount of bone formation was increased depending on time comparing 4 weeks and 12 weeks. At 12 weeks, lamellar bone was more formed along with the nano-micro titanium implant surfaces than 4 weeks. It indicated that nano-micro surface showed good result in terms of osseointegration.

Henry constant and isosteric heat at zero-loading for gas adsorption in carbon nanotubes.

PubMed

Do, D D; Do, H D; Wongkoblap, A; Nicholson, D

2008-12-28

The Henry constant and the isosteric heat of adsorption at zero loading in a carbon nanotube bundle are studied with Monte Carlo integration for the adsorption of gases over a range of temperatures. The spacing between nanotubes in a bundle is determined from the minimization of potential energy of interaction between these tubes. We study different tube configurations with bundles of 2, 3, 4 and 7 tubes. Depending on the configuration it is found that the spacing is of between 0.31 to 0.333 nm, and this falls within the range reported in the literature. The Henry constant has been carefully defined so that it will not become negative at high temperatures. This is done with the aid of accessible volume, rather than the usual absolute void volume. We show that linearity of the van't Hoff plot for the Henry constant is not strictly followed. Furthermore the slope of this plot is not equal to the isosteric heat of adsorption at zero loading, which is found to be a strong function of temperature. From the results we find that the Henry constant and the heat of adsorption depend on the tube configuration. In general the adsorption in the cusp interstices is strongest followed by that inside the tube and finally on the outer surface. However for very small tubes adsorption occurs inside the tube first. For molecules with orientation, the behaviour is even more interesting and the shape of the isosteric heat versus temperature depends on the degree of orientation, tube configuration and the domain of adsorption (interstices, inside the tube and on the outer surface).

Time as an Observable in Nonrelativistic Quantum Mechanics

NASA Technical Reports Server (NTRS)

Hahne, G. E.

2003-01-01

The argument follows from the viewpoint that quantum mechanics is taken not in the usual form involving vectors and linear operators in Hilbert spaces, but as a boundary value problem for a special class of partial differential equations-in the present work, the nonrelativistic Schrodinger equation for motion of a structureless particle in four- dimensional space-time in the presence of a potential energy distribution that can be time-as well as space-dependent. The domain of interest is taken to be one of two semi-infinite boxes, one bounded by two t=constant planes and the other by two t=constant planes. Each gives rise to a characteristic boundary value problem: one in which the initial, input values on one t=constant wall are given, with zero asymptotic wavefunction values in all spatial directions, the output being the values on the second t=constant wall; the second with certain input values given on both z=constant walls, with zero asymptotic values in all directions involving time and the other spatial coordinates, the output being the complementary values on the z=constant walls. The first problem corresponds to ordinary quantum mechanics; the second, to a fully time-dependent version of a problem normally considered only for the steady state (time-independent Schrodinger equation). The second problem is formulated in detail. A conserved indefinite metric is associated with space-like propagation, where the sign of the norm of a unidirectional state corresponds to its spatial direction of travel.

Oceanic lithosphere and asthenosphere - Thermal and mechanical structure

NASA Technical Reports Server (NTRS)

Schubert, G.; Yuen, D. A.; Froidevaux, C.

1976-01-01

A coupled thermomechanical subsolidus model of the oceanic lithosphere and asthenosphere is developed which includes vertical heat conduction, a temperature-dependent thermal conductivity, heat advection by a horizontal and vertical mass flow that depends on depth and age, contributions of viscous dissipation or shear heating, a linear or nonlinear deformation law relating shear stress and strain rate, as well as a temperature- and pressure-dependent viscosity. The model requires a constant horizontal velocity and temperature at the surface, but zero horizontal velocity and constant temperature at great depths. The depth- and age-dependent temperature, horizontal and vertical velocities, and viscosity structure of the lithosphere and asthenosphere are determined along with the age-dependent shear stress in those two zones. The ocean-floor topography, oceanic heat flow, and lithosphere thickness are deduced as functions of ocean-floor age; seismic velocity profiles which exhibit a marked low-velocity zone are constructed from the age-dependent geotherms and assumed values of the elastic parameters. It is found that simple boundary-layer cooling determines the thermal structure at young ages, while effects of viscous dissipation become more important at older ages.

On the penetration of a hot diapir through a strongly temperature-dependent viscosity medium

NASA Technical Reports Server (NTRS)

Daly, S. F.; Raefsky, A.

1985-01-01

The ascent of a hot spherical body through a fluid with a strongly temperature-dependent viscosity has been studied using an axisymmetric finite element method. Numerical solutions range over Peclet numbers of 0.1 - 1000 from constant viscosity up to viscosity variations of 100,000. Both rigid and stress-free boundary conditions were applied at the surface of the sphere. The dependence of drag on viscosity variation was shown to have no dependence on the stress boundary condition except for a Stokes flow scaling factor. A Nusselt number parameterization based on the stress-free constant viscosity functional dependence on the Peclet number scaled by a parameter depending on the viscosity structure fits both stress-free and rigid boundary condition data above viscosity variations of 100. The temperature scale height was determined as a function of sphere radius. For the simple physical model studied in this paper pre-heating is required to reduce the ambient viscosity of the country rock to less than 10 to the 22nd sq cm/s in order for a 10 km diapir to penetrate a distance of several radii.

Calibration of the k- ɛ model constants for use in CFD applications

NASA Astrophysics Data System (ADS)

Glover, Nina; Guillias, Serge; Malki-Epshtein, Liora

2011-11-01

The k- ɛ turbulence model is a popular choice in CFD modelling due to its robust nature and the fact that it has been well validated. However it has been noted in previous research that the k- ɛ model has problems predicting flow separation as well as unconfined and transient flows. The model contains five empirical model constants whose values were found through data fitting for a wide range of flows (Launder 1972) but ad-hoc adjustments are often made to these values depending on the situation being modeled. Here we use the example of flow within a regular street canyon to perform a Bayesian calibration of the model constants against wind tunnel data. This allows us to assess the sensitivity of the CFD model to changes in these constants, find the most suitable values for the constants as well as quantifying the uncertainty related to the constants and the CFD model as a whole.

Constant electrical resistivity of Ni along the melting boundary up to 9 GPa

NASA Astrophysics Data System (ADS)

Silber, Reynold E.; Secco, Richard A.; Yong, Wenjun

2017-07-01

Characterization of transport properties of liquid Ni at high pressures has important geophysical implications for terrestrial planetary interiors, because Ni is a close electronic analogue of Fe and it is also integral to Earth's core. We report measurements of the electrical resistivity of solid and liquid Ni at pressures 3-9 GPa using a 3000 t multianvil large volume press. A four-wire method, in conjunction with a rapid acquisition meter and polarity switch, was used to overcome experimental challenges such as melt containment and maintaining sample geometry and to mitigate the extreme reactivity/solubility of liquid Ni with most thermocouple and electrode materials. Thermal conductivity is calculated using the Wiedemann-Franz law. Electrical resistivity of solid Ni exhibits the expected P dependence and is consistent with earlier experimental values. Within experimental uncertainties, our results indicate that resistivity of liquid Ni remains invariant along the P-dependent melting boundary, which is in disagreement with earlier prediction for liquid transition metals. The potential reasons for such behavior are examined qualitatively through the impact of P-independent local short-range ordering on electron mean free path and the possibility of constant Fermi surface at the onset of Ni melting. Correlation among metals obeying the Kadowaki-Woods ratio and the group of late transition metals with unfilled d-electron band displaying anomalously shallow melting curves suggests that on the melting boundary, Fe may exhibit the same resistivity behavior as Ni. This could have important implications for the heat flow in the Earth's core.

An ongoing process: a qualitative study of how the alcohol-dependent free themselves of addiction through progressive abstinence.

PubMed

Yeh, Mei-Yu; Che, Hui-Lian; Wu, Shu-Mei

2009-11-24

Most people being treated for alcoholism are unable to successfully quit drinking within their treatment programs. In few cases do we know the full picture of how abstinence is achieved in Taiwan. We tracked processes of abstinence in alcohol-dependency disorders, based on study evidence and results. This research explores the process of recovery from the viewpoint of the alcohol-dependent. Semi-structured interviews were conducted in two different settings, using purpose sampling, during 2003-2004. The data were analyzed using content analysis. Participants were 32 adults, purposefully selected from an Alcoholics Anonymous group and a psychiatric hospital in North Taiwan. We found that the abstinence process is an ongoing process, in which the alcohol-dependent free themselves of addiction progressively. This process never ends or resolves in complete recovery. We have identified three stages in the struggle against alcoholism: the Indulgence, Ambivalence and Attempt (IAA) cycle, in which the sufferer is trapped in a cycle of attempting to give up and failing; the Turning Point, in which a Personal Nadir is reached, and the Ongoing Process of abstinence, in which a constant effort is made to remain sober through willpower and with the help of support groups. We also discuss Influencing Factors that can derail abstinence attempts, pushing the sufferer back into the IAA cycle. This study provides important points of reference for alcohol and drug service workers and community healthcare professionals in Taiwan, casting light on the abstinence process and providing a basis for intervention or rehabilitation services.

An ongoing process: A qualitative study of how the alcohol-dependent free themselves of addiction through progressive abstinence

PubMed Central

2009-01-01

Background Most people being treated for alcoholism are unable to successfully quit drinking within their treatment programs. In few cases do we know the full picture of how abstinence is achieved in Taiwan. We tracked processes of abstinence in alcohol-dependency disorders, based on study evidence and results. This research explores the process of recovery from the viewpoint of the alcohol-dependent. Methods Semi-structured interviews were conducted in two different settings, using purpose sampling, during 2003-2004. The data were analyzed using content analysis. Participants were 32 adults, purposefully selected from an Alcoholics Anonymous group and a psychiatric hospital in North Taiwan. Results We found that the abstinence process is an ongoing process, in which the alcohol-dependent free themselves of addiction progressively. This process never ends or resolves in complete recovery. We have identified three stages in the struggle against alcoholism: the Indulgence, Ambivalence and Attempt (IAA) cycle, in which the sufferer is trapped in a cycle of attempting to give up and failing; the Turning Point, in which a Personal Nadir is reached, and the Ongoing Process of abstinence, in which a constant effort is made to remain sober through willpower and with the help of support groups. We also discuss Influencing Factors that can derail abstinence attempts, pushing the sufferer back into the IAA cycle. Conclusion This study provides important points of reference for alcohol and drug service workers and community healthcare professionals in Taiwan, casting light on the abstinence process and providing a basis for intervention or rehabilitation services. PMID:19930698

Frustration in protein elastic network models

NASA Astrophysics Data System (ADS)

Lezon, Timothy; Bahar, Ivet

2010-03-01

Elastic network models (ENMs) are widely used for studying the equilibrium dynamics of proteins. The most common approach in ENM analysis is to adopt a uniform force constant or a non-specific distance dependent function to represent the force constant strength. Here we discuss the influence of sequence and structure in determining the effective force constants between residues in ENMs. Using a novel method based on entropy maximization, we optimize the force constants such that they exactly reporduce a subset of experimentally determined pair covariances for a set of proteins. We analyze the optimized force constants in terms of amino acid types, distances, contact order and secondary structure, and we demonstrate that including frustrated interactions in the ENM is essential for accurately reproducing the global modes in the middle of the frequency spectrum.

Kinetics of beta-haematin formation from suspensions of haematin in aqueous benzoic acid.

PubMed

Egan, Timothy J; Tshivhase, Mmboneni G

2006-11-14

Kinetics of beta-haematin (synthetic malaria pigment) formation from haematin have been studied in the presence of aqueous benzoic acid and derivatives of benzoic acid. Formation of the beta-haematin product is demonstrated by X-ray diffraction and IR spectroscopy. Reactions were followed by determining the fraction of unreacted haematin at various time points during the process via reaction of extracted aliquots with pyridine. The kinetics can be fitted to the Avrami equation, indicating that the process involves nucleation and growth. Reaction kinetics in stirred benzoic acid are similar to those previously observed in acetic acid, except that benzoic acid is far more active in promoting the reaction than acetic acid. The reaction reaches completion within 2 h in the presence of 0.050 M benzoic acid (pH 4.5, 60 degrees C). This compares with 1 h in the presence of 4.5 M acetic acid and 4 h in the presence of 2 M acetic acid. The reaction rate in benzoic acid is not affected if the stirring rate is decreased to zero, but very vigorous stirring appears to disrupt nucleation. The rate constant for beta-haematin formation in benzoic acid has a linear dependence on benzoic acid concentration and follows Arrhenius behaviour with temperature. There is a bell-shaped dependence on pH. This suggests that the haematin species in which one propionate group is protonated and the other is deprotonated is optimal for beta-haematin formation. When the reaction is conducted in para-substituted benzoic acid derivatives, the log of the rate constant increases linearly with the Hammett constant. These findings suggest that the role of the carboxylic acid may be to disrupt hydrogen bonding and pi-stacking in haematin, facilitating conversion to beta-haematin. The large activation energy for conversion of precipitated haematin to beta-haematin suggests that the reaction in vivo most likely involves direct nucleation from solution and probably does not occur in aqueous medium.

Kinetics of photoinduced electron transfer reactions of ruthenium(II) complexes and phenols, tyrosine, N-acetyl-tyrosine and tryptophan in aqueous solutions measured with modulated fluorescence spectroscopy.

PubMed

Nguyen, Truong X; Landgraf, Stephan; Grampp, Günter

2017-01-01

Photooxidation kinetics of phenol, 1-naphthol, 2-naphthol, tyrosine (TyrOH) and N-acetyl-tyrosine (AcTyrOH), tryptophan (TrpH) by ruthenium(II) polypyridyl complexes: [Ru(bpy) 3 ]Cl 2 (1), [Ru(phen) 3 ]Cl 2 (2), [Ru(bpy)(phen)(bpg)]Cl 2 (3), and [Ru(dpq) 2 (bxbg)]Cl 2 (4) where bpy is 2,2'-bipyridine, phen - 1,10-phenanthroline, bpg - bipyridine-glycoluril, dpq - dipyrido[3,2-d:2',3'-f]quinoxaline, and bxbg - bis(o-xylene)bipyridine-glycoluril are investigated. Rate constants have been measured by steady-state luminescence and phase-modulation fluorometry in aqueous solutions at different pH's. The rates for the oxidation of the phenols and phenolic aromatic amino acids spreads over a wide range from 4.2×10 6 to 6.8×10 9 M -1 s -1 , depending on pH and the nature of solutes. At pH>pK a of the quenchers, the presence of reactive species (PhO - ) in the alkaline solutions is accounted for the rapid ET rates. In the pH range between 4 and 10 (pH

Properties of water along the liquid-vapor coexistence curve via molecular dynamics simulations using the polarizable TIP4P-QDP-LJ water model

PubMed Central

Bauer, Brad A.; Patel, Sandeep

2009-01-01

We present an extension of the TIP4P-QDP model, TIP4P-QDP-LJ, that is designed to couple changes in repulsive and dispersive nonbond interactions to changes in polarizability. Polarizability is intimately related to the dispersion component of classical force field models of interactions, and we explore the effect of incorporating this connection explicitly on properties along the liquid-vapor coexistence curve of pure water. Parametrized to reproduce condensed-phase liquid water properties at 298 K, the TIP4P-QDP-LJ model predicts density, enthalpy of vaporization, self-diffusion constant, and the dielectric constant at ambient conditions to about the same accuracy as TIP4P-QDP but shows remarkable improvement in reproducing the liquid-vapor coexistence curve. TIP4P-QDP-LJ predicts critical constants of Tc=623 K, ρc=0.351 g∕cm3, and Pc=250.9 atm, which are in good agreement with experimental values of Tc=647.1 K, ρc=0.322 g∕cm3, and Pc=218 atm, respectively. Applying a scaling factor correction (obtained by fitting the experimental vapor-liquid equilibrium data to the law of rectilinear diameters using a three-term Wegner expansion) the model predicts critical constants (Tc=631 K and ρc=0.308 g∕cm3). Dependence of enthalpy of vaporization, self-diffusion constant, surface tension, and dielectric constant on temperature are shown to reproduce experimental trends. We also explore the interfacial potential drop across the liquid-vapor interface for the temperatures studied. The interfacial potential demonstrates little temperature dependence at lower temperatures (300–450 K) and significantly enhanced (exponential) dependence at elevated temperatures. Terms arising from the decomposition of the interfacial potential into dipole and quadrupole contributions are shown to monotonically approach zero as the temperature approaches the critical temperature. Results of this study suggest that self-consistently treating the coupling of phase-dependent polarizability with dispersion interactions in classical water force fields may be an important effect for the extension of polarizable water force fields to reproduce properties along the liquid-vapor coexistence envelope as well as near critical conditions. More importantly, the present study demonstrates the rather remarkable transferability of a water model parametrized to a single state point to other thermodynamic states. Further studies are recommended. PMID:19725623

Properties of water along the liquid-vapor coexistence curve via molecular dynamics simulations using the polarizable TIP4P-QDP-LJ water model.

PubMed

Bauer, Brad A; Patel, Sandeep

2009-08-28

We present an extension of the TIP4P-QDP model, TIP4P-QDP-LJ, that is designed to couple changes in repulsive and dispersive nonbond interactions to changes in polarizability. Polarizability is intimately related to the dispersion component of classical force field models of interactions, and we explore the effect of incorporating this connection explicitly on properties along the liquid-vapor coexistence curve of pure water. Parametrized to reproduce condensed-phase liquid water properties at 298 K, the TIP4P-QDP-LJ model predicts density, enthalpy of vaporization, self-diffusion constant, and the dielectric constant at ambient conditions to about the same accuracy as TIP4P-QDP but shows remarkable improvement in reproducing the liquid-vapor coexistence curve. TIP4P-QDP-LJ predicts critical constants of T(c)=623 K, rho(c)=0.351 g/cm(3), and P(c)=250.9 atm, which are in good agreement with experimental values of T(c)=647.1 K, rho(c)=0.322 g/cm(3), and P(c)=218 atm, respectively. Applying a scaling factor correction (obtained by fitting the experimental vapor-liquid equilibrium data to the law of rectilinear diameters using a three-term Wegner expansion) the model predicts critical constants (T(c)=631 K and rho(c)=0.308 g/cm(3)). Dependence of enthalpy of vaporization, self-diffusion constant, surface tension, and dielectric constant on temperature are shown to reproduce experimental trends. We also explore the interfacial potential drop across the liquid-vapor interface for the temperatures studied. The interfacial potential demonstrates little temperature dependence at lower temperatures (300-450 K) and significantly enhanced (exponential) dependence at elevated temperatures. Terms arising from the decomposition of the interfacial potential into dipole and quadrupole contributions are shown to monotonically approach zero as the temperature approaches the critical temperature. Results of this study suggest that self-consistently treating the coupling of phase-dependent polarizability with dispersion interactions in classical water force fields may be an important effect for the extension of polarizable water force fields to reproduce properties along the liquid-vapor coexistence envelope as well as near critical conditions. More importantly, the present study demonstrates the rather remarkable transferability of a water model parametrized to a single state point to other thermodynamic states. Further studies are recommended.

[Comparative study of the repair of full thickness tear of the supraspinatus by means of "single row" or "suture bridge" techniques].

PubMed

Arroyo-Hernández, M; Mellado-Romero, M A; Páramo-Díaz, P; Martín-López, C M; Cano-Egea, J M; Vilá Y Rico, J

2015-01-01

The purpose of this study is to analyze if there is any difference between the arthroscopic reparation of full-thickness supraspinatus tears with simple row technique versus suture bridge technique. We accomplished a retrospective study of 123 patients with full-thickness supraspinatus tears between January 2009 and January 2013 in our hospital. There were 60 simple row reparations, and 63 suture bridge ones. The mean age in the simple row group was 62.9, and in the suture bridge group was 63.3 years old. There were more women than men in both groups (67%). All patients were studied using the Constant test. The mean Constant test in the suture bridge group was 76.7, and in the simple row group was 72.4. We have also accomplished a statistical analysis of each Constant item. Strength was higher in the suture bridge group, with a significant statistical difference (p 0.04). The range of movement was also greater in the suture bridge group, but was not statistically significant. Suture bridge technique has better clinical results than single row reparations, but the difference is not statistically significant (p = 0.298).

Quantifying the effect of varying GHG's concentration in Regional Climate Models

NASA Astrophysics Data System (ADS)

López-Romero, Jose Maria; Jerez, Sonia; Palacios-Peña, Laura; José Gómez-Navarro, Juan; Jiménez-Guerrero, Pedro; Montavez, Juan Pedro

2017-04-01

Regional Climate Models (RCMs) are driven at the boundaries by Global Circulation Models (GCM), and in the particular case of Climate Change projections, such simulations are forced by varying greenhouse gases (GHGs) concentrations. In hindcast simulations driven by reanalysis products, the climate change signal is usually introduced in the assimilation process as well. An interesting question arising in this context is whether GHGs concentrations have to be varied within the RCMs model itself, or rather they should be kept constant. Some groups keep the GHGs concentrations constant under the assumption that information about climate change signal is given throughout the boundaries; sometimes certain radiation parameterization schemes do not permit such changes. Other approaches vary these concentrations arguing that this preserves the physical coherence respect to the driving conditions for the RCM. This work aims to shed light on this topic. For this task, various regional climate simulations with the WRF model for the 1954-2004 period have been carried out for using a Euro-CORDEX compliant domain. A series of simulations with constant and variable GHGs have been performed using both, a GCM (ECHAM6-OM) and a reanalysis product (ERA-20C) data. Results indicate that there exist noticeable differences when introducing varying GHGs concentrations within the RCM domain. The differences in 2-m temperature series between the experiments with varying or constant GHGs concentration strongly depend on the atmospheric conditions, appearing a strong interannual variability. This suggests that short-term experiments are not recommended if the aim is to assess the role of varying GHGs. In addition, and consistently in both GCM and reanalysis-driven experiments, the magnitude of temperature trends, as well as the spatial pattern represented by varying GHGs experiment, are closer to the driving dataset than in experiments keeping constant the GHGs concentration. These results point towards the need for the inclusion of varying GHGs concentration within the RCM itself when dynamically downscaling global datasets, both in GCM and hindcast simulations.

On the dependence of the domain of values of functionals of hypersonic aerodynamics on controls

NASA Astrophysics Data System (ADS)

Bilchenko, Grigory; Bilchenko, Nataly

2018-05-01

The properties of mathematical model of control of heat and mass transfer in laminar boundary layer on permeable cylindrical and spherical surfaces of the hypersonic aircraft are considered. Dependences of hypersonic aerodynamics functionals (the total heat flow and the total Newton friction force) on controls (the blowing into boundary layer, the temperature factor, the magnetic field) are investigated. The domains of allowed values of functionals of hypersonic aerodynamics are obtained. The results of the computational experiments are presented: the dependences of total heat flow on controls; the dependences of total Newton friction force on controls; the mutual dependences of functionals (as the domains of allowed values "Heat and Friction"); the dependences of blowing system power on controls. The influences of magnetic field and dissociation on the domain of "Heat and Friction" allowed values are studied. It is proved that for any fixed constant value of magnetic field the blowing system power is a symmetric function of constant dimensionless controls (the blowing into boundary layer and the temperature factor). It is shown that the obtained domain of allowed values of functionals of hypersonic aerodynamics depending on permissible range of controls may be used in engineering.

Baseline-dependent sampling and windowing for radio interferometry: data compression, field-of-interest shaping, and outer field suppression

NASA Astrophysics Data System (ADS)

Atemkeng, M.; Smirnov, O.; Tasse, C.; Foster, G.; Keimpema, A.; Paragi, Z.; Jonas, J.

2018-07-01

Traditional radio interferometric correlators produce regular-gridded samples of the true uv-distribution by averaging the signal over constant, discrete time-frequency intervals. This regular sampling and averaging then translate to be irregular-gridded samples in the uv-space, and results in a baseline-length-dependent loss of amplitude and phase coherence, which is dependent on the distance from the image phase centre. The effect is often referred to as `decorrelation' in the uv-space, which is equivalent in the source domain to `smearing'. This work discusses and implements a regular-gridded sampling scheme in the uv-space (baseline-dependent sampling) and windowing that allow for data compression, field-of-interest shaping, and source suppression. The baseline-dependent sampling requires irregular-gridded sampling in the time-frequency space, i.e. the time-frequency interval becomes baseline dependent. Analytic models and simulations are used to show that decorrelation remains constant across all the baselines when applying baseline-dependent sampling and windowing. Simulations using MeerKAT telescope and the European Very Long Baseline Interferometry Network show that both data compression, field-of-interest shaping, and outer field-of-interest suppression are achieved.

A root-mean-square pressure fluctuations model for internal flow applications

NASA Technical Reports Server (NTRS)

Chen, Y. S.

1985-01-01

A transport equation for the root-mean-square pressure fluctuations of turbulent flow is derived from the time-dependent momentum equation for incompressible flow. Approximate modeling of this transport equation is included to relate terms with higher order correlations to the mean quantities of turbulent flow. Three empirical constants are introduced in the model. Two of the empirical constants are estimated from homogeneous turbulence data and wall pressure fluctuations measurements. The third constant is determined by comparing the results of large eddy simulations for a plane channel flow and an annulus flow.

The p- T phase diagram of KNbO 3 by a dielectric constant measurement

NASA Astrophysics Data System (ADS)

Kobayashi, Y.; Endo, S.; Deguchi, K.; Ming, L. C.; Zou, G.

2001-11-01

A dielectric constant measurement was carried out on perovskite-type ferroelectrics KNbO 3 over a wide range of temperature under high pressure. The temperature- and pressure-dependence of the dielectric constant clarified that all temperatures of the transitions from the ferroelectric rhombohedral to orthorhombic, to tetragonal and then to the paraelectric cubic phase, decrease with increasing pressure. These results indicate that the orthorhombic-tetragonal transition takes place at 8.5 GPa and the tetragonal-cubic transition at 11 GPa, at room temperature.

pH-Dependence of Binding Constants and Desorption Rates of Phosphonate- and Hydroxamate-Anchored [Ru(bpy)3]2+ on TiO2 and WO3.

PubMed

Esarey, Samuel L; Bartlett, Bart M

2018-04-17

The binding constants and rate constants for desorption of the modified molecular dye [Ru(bpy) 3 ] 2+ anchored by either phosphonate or hydroxamate on the bipyridine ligand to anatase TiO 2 and WO 3 have been measured. In aqueous media at pH 1-10, repulsive electrostatic interactions between the negatively charged anchor and the negatively charged surface govern phosphonate desorption under neutral and basic conditions for TiO 2 anatase due to the high acidity of phosphonic acid (p K a,4 = 5.1). In contrast, the lower acidity of hydroxamate (p K a,1 = 6.5, p K a,2 = 9.1) leads to little change in adsorption/desorption properties as a function of pH from 1 to 7. The binding constant for hydroxamate is 10 3 in water, independent of pH in this range. These results are true for WO 3 as well, but are not reported at pH > 4 due to its Arrhenius acidity. Kinetics for desorption as a function of pH are reported, with a proposed mechanism for phosphonate desorption at high pH being the electrostatic repulsion of negative charges between the surface and the anionic anchor. Further, the hydroxamic acid anchor itself is likely the site of quasi-reversible redox activity in [Ru(bpy) 2 (2,2'-bpy-4,4'-(C(O)N(OH)) 2 )] 2+ , which does not lead to any measurable deterioration of the complex within 2 h of dark cyclic voltammogram scans in aqueous media. These results posit phosphonate as the preferred anchoring group under acidic conditions and hydroxamate for neutral/basic conditions.

A fast, parallel algorithm for distant-dependent calculation of crystal properties

NASA Astrophysics Data System (ADS)

Stein, Matthew

2017-12-01

A fast, parallel algorithm for distant-dependent calculation and simulation of crystal properties is presented along with speedup results and methods of application. An illustrative example is used to compute the Lennard-Jones lattice constants up to 32 significant figures for 4 ≤ p ≤ 30 in the simple cubic, face-centered cubic, body-centered cubic, hexagonal-close-pack, and diamond lattices. In most cases, the known precision of these constants is more than doubled, and in some cases, corrected from previously published figures. The tools and strategies to make this computation possible are detailed along with application to other potentials, including those that model defects.

Ultra High Strain Rate Nanoindentation Testing.

PubMed

Sudharshan Phani, Pardhasaradhi; Oliver, Warren Carl

2017-06-17

Strain rate dependence of indentation hardness has been widely used to study time-dependent plasticity. However, the currently available techniques limit the range of strain rates that can be achieved during indentation testing. Recent advances in electronics have enabled nanomechanical measurements with very low noise levels (sub nanometer) at fast time constants (20 µs) and high data acquisition rates (100 KHz). These capabilities open the doors for a wide range of ultra-fast nanomechanical testing, for instance, indentation testing at very high strain rates. With an accurate dynamic model and an instrument with fast time constants, step load tests can be performed which enable access to indentation strain rates approaching ballistic levels (i.e., 4000 1/s). A novel indentation based testing technique involving a combination of step load and constant load and hold tests that enables measurement of strain rate dependence of hardness spanning over seven orders of magnitude in strain rate is presented. A simple analysis is used to calculate the equivalent uniaxial response from indentation data and compared to the conventional uniaxial data for commercial purity aluminum. Excellent agreement is found between the indentation and uniaxial data over several orders of magnitude of strain rate.

Rate constants for the reactions of OH with CH3Cl, CH2Cl2, CHCl3, and CH3Br

NASA Technical Reports Server (NTRS)

Hsu, K.-J.; Demore, W. B.

1994-01-01

Rate constants for the reactions of OH with CH3Cl, CH2Cl2, CHCl3, and CH3Br have been measured by a relative rate technique in which the reaction rate of each compound was compared to that of HFC-152a (CH3CHF2) and (for CH2Cl2) HFC-161 (CH3CH2F). Using absolute rate constants for HFC-152a and HFC-161, which we have determined relative to those for CH4, CH3CCl3, and C2H6, temperature dependent rate constants of both compounds were derived. The derived rate constant for CH3Br is in good agreement with recent absolute measurements. However, for the chloromethanes all the rate constants are lower at atmospheric temperatures than previously reported, especially for CH2Cl2 where the present rate constant is about a factor of 1.6 below the JPL 92-20 value. The new rate constant appears to resolve a discrepancy between the observed atmospheric concentrations and those calculated from the previous rate constant and estimated release rates.

Ultrafast electronic relaxation in superheated bismuth

NASA Astrophysics Data System (ADS)

Gamaly, E. G.; Rode, A. V.

2013-01-01

Interaction of moving electrons with vibrating ions in the lattice forms the basis for many physical properties from electrical resistivity and electronic heat capacity to superconductivity. In ultrafast laser interaction with matter the electrons are heated much faster than the electron-ion energy equilibration, leading to a two-temperature state with electron temperature far above that of the lattice. The rate of temperature equilibration is governed by the strength of electron-phonon energy coupling, which is conventionally described by a coupling constant, neglecting the dependence on the electron and lattice temperature. The application of this constant to the observations of fast relaxation rate led to a controversial notion of ‘ultra-fast non-thermal melting’ under extreme electronic excitation. Here we provide theoretical grounds for a strong dependence of the electron-phonon relaxation time on the lattice temperature. We show, by taking proper account of temperature dependence, that the heating and restructuring of the lattice occurs much faster than were predicted on the assumption of a constant, temperature independent energy coupling. We applied the temperature-dependent momentum and energy transfer time to experiments on fs-laser excited bismuth to demonstrate that all the observed ultra-fast transformations of the transient state of bismuth are purely thermal in nature. The developed theory, when applied to ultrafast experiments on bismuth, provides interpretation of the whole variety of transient phase relaxation without the non-thermal melting conjecture.

Bimetallic nanoparticles synthesized in microemulsions: A computer simulation study on relationship between kinetics and metal segregation.

PubMed

Tojo, Concha; Buceta, David; López-Quintela, M Arturo

2018-01-15

Computer simulations were carried out to study the origin of the different metal segregation showed by bimetallic nanoparticles synthesized in microemulsions. Our hypothesis is that the kinetics of nanoparticle formation in microemulsions has to be considered on terms of two potentially limiting factors, chemical reaction itself and the rate of reactants exchange between micelles. From the kinetic study it is deduced that chemical reduction in microemulsions is a pseudo first-order process, but not from the beginning. At the initial stage of the synthesis, redistribution of reactants between micelles is controlled by the intermicellar exchange rate, meanwhile the core and middle layers are being built. This exchange control has a different impact depending on the reduction rate of the particular metal in relation to the intermicellar exchange rate. For the case of Au/Pt nanoparticles, the kinetic constant of Au (fast reduction) is strongly dependent on intermicellar exchange rate and reactant concentration. On the contrary, the kinetic constant of Pt (slower reduction) remains constant. Therefore, the fact that the reaction takes place in a microemulsion affects more or less depending on the reduction rate of the metals. As a consequence, the final nanostructure not only depends on difference between the reduction rates of both metals, but also on the reduction rate of each metal in relation to the intermicellar exchange rate. Copyright © 2017 Elsevier Inc. All rights reserved.

Linear response of mutans streptococci to increasing frequency of xylitol chewing gum use: a randomized controlled trial [ISRCTN43479664

PubMed Central

Ly, Kiet A; Milgrom, Peter; Roberts, Marilyn C; Yamaguchi, David K; Rothen, Marilynn; Mueller, Greg

2006-01-01

Background Xylitol is a naturally occurring sugar substitute that has been shown to reduce the level of mutans streptococci in plaque and saliva and to reduce tooth decay. It has been suggested that the degree of reduction is dependent on both the amount and the frequency of xylitol consumption. For xylitol to be successfully and cost-effectively used in public health prevention strategies dosing and frequency guidelines should be established. This study determined the reduction in mutans streptococci levels in plaque and unstimulated saliva to increasing frequency of xylitol gum use at a fixed total daily dose of 10.32 g over five weeks. Methods Participants (n = 132) were randomized to either active groups (10.32 g xylitol/day) or a placebo control (9.828 g sorbitol and 0.7 g maltitol/day). All groups chewed 12 pieces of gum per day. The control group chewed 4 times/day and active groups chewed xylitol gum at a frequency of 2 times/day, 3 times/day, or 4 times/day. The 12 gum pieces were evenly divided into the frequency assigned to each group. Plaque and unstimulated saliva samples were taken at baseline and five-weeks and were cultured on modified Mitis Salivarius agar for mutans streptococci enumeration. Results There were no significant differences in mutans streptococci level among the groups at baseline. At five-weeks, mutans streptococci levels in plaque and unstimulated saliva showed a linear reduction with increasing frequency of xylitol chewing gum use at the constant daily dose. Although the difference observed for the group that chewed xylitol 2 times/day was consistent with the linear model, the difference was not significant. Conclusion There was a linear reduction in mutans streptococci levels in plaque and saliva with increasing frequency of xylitol gum use at a constant daily dose. Reduction at a consumption frequency of 2 times per day was small and consistent with the linear-response line but was not statistically significant. PMID:16556326

Characterization of Full Set Material Constants and Their Temperature Dependence for Piezoelectric Materials Using Resonant Ultrasound Spectroscopy

PubMed Central

Tang, Liguo; Cao, Wenwu

2016-01-01

During the operation of high power electromechanical devices, a temperature rise is unavoidable due to mechanical and electrical losses, causing the degradation of device performance. In order to evaluate such degradations using computer simulations, full matrix material properties at elevated temperatures are needed as inputs. It is extremely difficult to measure such data for ferroelectric materials due to their strong anisotropic nature and property variation among samples of different geometries. Because the degree of depolarization is boundary condition dependent, data obtained by the IEEE (Institute of Electrical and Electronics Engineers) impedance resonance technique, which requires several samples with drastically different geometries, usually lack self-consistency. The resonant ultrasound spectroscopy (RUS) technique allows the full set material constants to be measured using only one sample, which can eliminate errors caused by sample to sample variation. A detailed RUS procedure is demonstrated here using a lead zirconate titanate (PZT-4) piezoceramic sample. In the example, the complete set of material constants was measured from room temperature to 120 °C. Measured free dielectric constants and  were compared with calculated ones based on the measured full set data, and piezoelectric constants d15 and d33 were also calculated using different formulas. Excellent agreement was found in the entire range of temperatures, which confirmed the self-consistency of the data set obtained by the RUS. PMID:27168336

Developmental times and life table statistics of Aulacorthum solani (Hemiptera: Aphididae) at six constant temperatures, with recommendations on the application of temperature-dependent development models

USDA-ARS?s Scientific Manuscript database

Developmental rates and age-specific life tables were determined for Aulacorthum solani (Kaltenbach) (known as foxglove aphid or glasshouse potato aphid) at 6 constant temperatures feeding on pansy (Viola × wittrockiana) (Gams.). Previously, there were no complete life table studies of this species...

Polymerized PolyHEMA photonic crystals: pH and ethanol sensor materials.

PubMed

Xu, Xiangling; Goponenko, Alexander V; Asher, Sanford A

2008-03-12

The surface of monodisperse silica particles synthesized using the Stober process were coated with a thin layer of polystyrene. Surface charge groups were attached by a grafting polymerization of styrene sulfonate. The resulting highly charged monodisperse silica particles self-assemble into crystalline colloidal arrays (CCA) in deionized water. We polymerized hydroxyethyl methacrylate (HEMA) around the CCA to form a HEMA-polymerized crystalline colloidal array (PCCA). Hydrofluoric acid was utilized to etch out the silica particles to produce a three-dimensional periodic array of voids in the HEMA PCCA. The diffraction from the embedded CCA sensitively monitors the concentration of ethanol in water because the HEMA PCCA shows a large volume dependence on ethanol due to a decreased Flory-Huggins mixing parameter. Between pure water and 40% ethanol the diffraction shifts across the entire visible spectral region. We accurately modeled the dependence of the diffraction wavelength on ethanol concentration using Flory theory. We also fabricated a PCCA (which responds to pH changes in both low and high ionic strength solutions) by utilizing a second polymerization to incorporate carboxyl groups into the HEMA PCCA. We were also able to model the pH dependence of diffraction of the HEMA PCCA by using Flory theory. An unusual feature of the pH response is a hysteresis in response to titration to higher and lower pH. This hysteresis results from the formation of a Donnan potential at high pH which shifts the ionic equilibrium. The kinetics of equilibration is very slow due to the ultralow diffusion constant of protons in the carboxylated PCCA as predicted earlier by the Tanaka group.

Theory for rates, equilibrium constants, and Brønsted slopes in F1-ATPase single molecule imaging experiments

PubMed Central

Volkán-Kacsó, Sándor; Marcus, Rudolph A.

2015-01-01

A theoretical model of elastically coupled reactions is proposed for single molecule imaging and rotor manipulation experiments on F1-ATPase. Stalling experiments are considered in which rates of individual ligand binding, ligand release, and chemical reaction steps have an exponential dependence on rotor angle. These data are treated in terms of the effect of thermodynamic driving forces on reaction rates, and lead to equations relating rate constants and free energies to the stalling angle. These relations, in turn, are modeled using a formalism originally developed to treat electron and other transfer reactions. During stalling the free energy profile of the enzymatic steps is altered by a work term due to elastic structural twisting. Using biochemical and single molecule data, the dependence of the rate constant and equilibrium constant on the stall angle, as well as the Børnsted slope are predicted and compared with experiment. Reasonable agreement is found with stalling experiments for ATP and GTP binding. The model can be applied to other torque-generating steps of reversible ligand binding, such as ADP and Pi release, when sufficient data become available. PMID:26483483

Pressure dependence of the absolute rate constant for the reaction OH + C2H2 from 228 to 413K

NASA Technical Reports Server (NTRS)

Michael, J. V.; Nava, D. F.; Borokowski, R. P.; Payne, W. A.; Stief, L. J.

1980-01-01

The pressure dependence of absolute rate constants for the reaction of OH + C2H2 yields products has been examined at five temperatures ranging from 228 to 413 K. The experimental techniques which was used is flash photolysis-resonance fluoresence. OH was produced by water photolysis and hydroxyl resonance fluorescent photons were measured by multiscaling techniques. The results indicate that the low pressure bimolecular rate constant is 4 x 10 the the minus 13th power cu cm molecule (-1) s(-1) over the temperature range studied. A substantial increase in the bimolecular rate constant with an increase in pressure was observed at all temperatures except 228 K. This indicates the importance of initial adduct formation and subsequent stablization. The high pressure results are well represented by the Arrhenius expression (k sub bi) sub infinity = (6.83 + or - 1.19) x 10 to the minus 12th power exp(-646 + or - 47/T)cu cm molecule (-1) s(-1). The results are compared to previous investigated and are theoretically discussed. The implications of these results on modeling of terrestrial and planetary atmospheres and also in combustion chemistry are discussed.

Electronic transport in two-dimensional high dielectric constant nanosystems

DOE PAGES

Ortuño, M.; Somoza, A. M.; Vinokur, V. M.; ...

2015-04-10

There has been remarkable recent progress in engineering high-dielectric constant two dimensional (2D) materials, which are being actively pursued for applications in nanoelectronics in capacitor and memory devices, energy storage, and high-frequency modulation in communication devices. Yet many of the unique properties of these systems are poorly understood and remain unexplored. Here we report a numerical study of hopping conductivity of the lateral network of capacitors, which models two-dimensional insulators, and demonstrate that 2D long-range Coulomb interactions lead to peculiar size effects. We find that the characteristic energy governing electronic transport scales logarithmically with either system size or electrostatic screeningmore » length depending on which one is shorter. Our results are relevant well beyond their immediate context, explaining, for example, recent experimental observations of logarithmic size dependence of electric conductivity of thin superconducting films in the critical vicinity of superconductor-insulator transition where a giant dielectric constant develops. Our findings mark a radical departure from the orthodox view of conductivity in 2D systems as a local characteristic of materials and establish its macroscopic global character as a generic property of high-dielectric constant 2D nanomaterials.« less

Electronic transport in two-dimensional high dielectric constant nanosystems.

PubMed

Ortuño, M; Somoza, A M; Vinokur, V M; Baturina, T I

2015-04-10

There has been remarkable recent progress in engineering high-dielectric constant two dimensional (2D) materials, which are being actively pursued for applications in nanoelectronics in capacitor and memory devices, energy storage, and high-frequency modulation in communication devices. Yet many of the unique properties of these systems are poorly understood and remain unexplored. Here we report a numerical study of hopping conductivity of the lateral network of capacitors, which models two-dimensional insulators, and demonstrate that 2D long-range Coulomb interactions lead to peculiar size effects. We find that the characteristic energy governing electronic transport scales logarithmically with either system size or electrostatic screening length depending on which one is shorter. Our results are relevant well beyond their immediate context, explaining, for example, recent experimental observations of logarithmic size dependence of electric conductivity of thin superconducting films in the critical vicinity of superconductor-insulator transition where a giant dielectric constant develops. Our findings mark a radical departure from the orthodox view of conductivity in 2D systems as a local characteristic of materials and establish its macroscopic global character as a generic property of high-dielectric constant 2D nanomaterials.

Effect of cantilever geometry on the optical lever sensitivities and thermal noise method of the atomic force microscope.

PubMed

Sader, John E; Lu, Jianing; Mulvaney, Paul

2014-11-01

Calibration of the optical lever sensitivities of atomic force microscope (AFM) cantilevers is especially important for determining the force in AFM measurements. These sensitivities depend critically on the cantilever mode used and are known to differ for static and dynamic measurements. Here, we calculate the ratio of the dynamic and static sensitivities for several common AFM cantilevers, whose shapes vary considerably, and experimentally verify these results. The dynamic-to-static optical lever sensitivity ratio is found to range from 1.09 to 1.41 for the cantilevers studied - in stark contrast to the constant value of 1.09 used widely in current calibration studies. This analysis shows that accuracy of the thermal noise method for the static spring constant is strongly dependent on cantilever geometry - neglect of these dynamic-to-static factors can induce errors exceeding 100%. We also discuss a simple experimental approach to non-invasively and simultaneously determine the dynamic and static spring constants and optical lever sensitivities of cantilevers of arbitrary shape, which is applicable to all AFM platforms that have the thermal noise method for spring constant calibration.

Molecular dynamics simulations of thermally activated edge dislocation unpinning from voids in α -Fe

NASA Astrophysics Data System (ADS)

Byggmästar, J.; Granberg, F.; Nordlund, K.

2017-10-01

In this study, thermal unpinning of edge dislocations from voids in α -Fe is investigated by means of molecular dynamics simulations. The activation energy as a function of shear stress and temperature is systematically determined. Simulations with a constant applied stress are compared with dynamic simulations with a constant strain rate. We found that a constant applied stress results in a temperature-dependent activation energy. The temperature dependence is attributed to the elastic softening of iron. If the stress is normalized with the softening of the specific shear modulus, the activation energy is shown to be temperature-independent. From the dynamic simulations, the activation energy as a function of critical shear stress was determined using previously developed methods. The results from the dynamic simulations are in good agreement with the constant stress simulations, after the normalization. This indicates that the computationally more efficient dynamic method can be used to obtain the activation energy as a function of stress and temperature. The obtained relation between stress, temperature, and activation energy can be used to introduce a stochastic unpinning event in larger-scale simulation methods, such as discrete dislocation dynamics.

Model for temperature-dependent magnetization of nanocrystalline materials

NASA Astrophysics Data System (ADS)

Bian, Q.; Niewczas, M.

2015-01-01

A magnetization model of nanocrystalline materials incorporating intragrain anisotropies, intergrain interactions, and texture effects has been extended to include the thermal fluctuations. The method relies on the stochastic Landau-Lifshitz-Gilbert theory of magnetization dynamics and permits to study the magnetic properties of nanocrystalline materials at arbitrary temperature below the Currie temperature. The model has been used to determine the intergrain exchange constant and grain boundary anisotropy constant of nanocrystalline Ni at 100 K and 298 K. It is found that the thermal fluctuations suppress the strength of the intergrain exchange coupling and also reduce the grain boundary anisotropy. In comparison with its value at 2 K, the interparticle exchange constant decreases by 16% and 42% and the grain boundary anisotropy constant decreases by 28% and 40% at 100 K and 298 K, respectively. An application of the model to study the grain size-dependent magnetization indicates that when the thermal activation energy is comparable to the free energy of grains, the decrease in the grain size leads to the decrease in the magnetic permeability and saturation magnetization. The mechanism by which the grain size influences the magnetic properties of nc-Ni is discussed.

Temperature dependencies of Henry’s law constants for different plant sesquiterpenes

PubMed Central

Copolovici, Lucian; Niinemets, Ülo

2018-01-01

Sesquiterpenes are plant-produced hydrocarbons with important ecological functions in plant-to-plant and plant-to-insect communication, but due to their high reactivity they can also play a significant role in atmospheric chemistry. So far, there is little information of gas/liquid phase partition coefficients (Henry’s law constants) and their temperature dependencies for sesquiterpenes, but this information is needed for quantitative simulation of the release of sesquiterpenes from plants and modeling atmospheric reactions in different phases. In this study, we estimated Henry’s law constants (Hpc) and their temperature responses for 12 key plant sesquiterpenes with varying structure (aliphatic, mono-, bi- and tricyclic sesquiterpenes). At 25 °C, Henry’s law constants varied 1.4-fold among different sesquiterpenes, and the values were within the range previously observed for monocyclic monoterpenes. Hpc of sesquiterpenes exhibited a high rate of increase, on average ca. 1.5-fold with a 10 °C increase in temperature (Q10). The values of Q10 varied 1.2-fold among different sesquiterpenes. Overall, these data demonstrate moderately high variation in Hpc values and Hpc temperature responses among different sesquiterpenes. We argue that these variations can importantly alter the emission kinetics of sesquiterpenes from plants. PMID:26291755

Hyperinsulinemia prevents prolonged hyperglycemia after intense exercise in insulin-dependent diabetic subjects.

PubMed

Sigal, R J; Purdon, C; Fisher, S J; Halter, J B; Vranic, M; Marliss, E B

1994-10-01

Hyperglycemia with accompanying hyperinsulinemia occurs after brief, greater than 85% maximum oxygen consumption exercise to exhaustion in normal subjects and persists up to 60 min of recovery. To determine the importance of endogenous insulin secretion during and after intense exercise, responses to exercise of lean fit male post-absorptive insulin-dependent diabetes mellitus (IDDM) subjects, aged 18-34 yr, were compared with those of control subjects (C; n = 6). Three iv insulin protocols were employed: hyperglycemic (HG; n = 7) and euglycemic (EG1; n = 6) with constant insulin infusion, and euglycemic with doubled insulin infusion during recovery (EG2; n = 6). Overnight iv insulin was adjusted to achieve prolonged euglycemia (5.4 +/- 0.3 mmol/L) or hyperglycemia (8.6 +/- 0.3 mmol/L) before exercise. This allowed for comparisons between HG and EG1 (constant infusion) and between C and EG2 (to approximate physiological hyperinsulinemia by doubling the infusion rates at exhaustion for 56 +/- 7 min during recovery). Subjects exercised to 89-98% of their individual maximum oxygen consumption for 12.8 +/- 0.3 min. Glycemia increased to maximum values at 6 min of recovery (9.8 +/- 0.5 in HG, 6.9 +/- 0.4 in EG1, 7.3 +/- 0.3 in EG2, and 6.9 +/- 0.4 mmol/L in C). Whereas in EG2 and C, glucose returned to resting values in 50-80 min, it remained elevated at 120 min recovery in HG and EG1. During exercise, [3-3H]-glucose-determined glucose production increased markedly and exceeded disappearance in all groups, but less so in the HG subjects than in the other groups. An early recovery decline in glucose production did not differ among groups, but MCR (rate of glucose disappearance/glycemia) were markedly lower in HG and EG1, in whom plasma free insulin remained unchanged from 15 min of recovery onward (MCR, 1.6-1.9 vs. 2.3-2.8 mL/kg.min in C). Doubling the insulin infusion rate in EG2 restored the MCR response to that of C subjects. In summary, constant insulin infusion is insufficient to prevent prolonged postexercise hyperglycemia in IDDM subjects, even when provided at a rate sufficient to maintain normal resting glycemia and glucose turnover. The finding that increasing the rate of insulin infusion restored plasma glucose to normal in IDDM subjects suggests that the postexercise increase in insulin levels observed in normal subjects is essential to return plasma glucose to resting levels. Therefore, special strategies, differing from those for less strenuous exercise, are required for the management of insulin therapy in IDDM during and after intense exercise.

Influence of primary fragment excitation energy and spin distributions on fission observables

NASA Astrophysics Data System (ADS)

Litaize, Olivier; Thulliez, Loïc; Serot, Olivier; Chebboubi, Abdelaziz; Tamagno, Pierre

2018-03-01

Fission observables in the case of 252Cf(sf) are investigated by exploring several models involved in the excitation energy sharing and spin-parity assignment between primary fission fragments. In a first step the parameters used in the FIFRELIN Monte Carlo code "reference route" are presented: two parameters for the mass dependent temperature ratio law and two constant spin cut-off parameters for light and heavy fragment groups respectively. These parameters determine the initial fragment entry zone in excitation energy and spin-parity (E*, Jπ). They are chosen to reproduce the light and heavy average prompt neutron multiplicities. When these target observables are achieved all other fission observables can be predicted. We show here the influence of input parameters on the saw-tooth curve and we discuss the influence of a mass and energy-dependent spin cut-off model on gamma-rays related fission observables. The part of the model involving level densities, neutron transmission coefficients or photon strength functions remains unchanged.

Correlation between structural, electrical and magnetic properties of GdMnO3 bulk ceramics

NASA Astrophysics Data System (ADS)

Samantaray, S.; Mishra, D. K.; Pradhan, S. K.; Mishra, P.; Sekhar, B. R.; Behera, Debdhyan; Rout, P. P.; Das, S. K.; Sahu, D. R.; Roul, B. K.

2013-08-01

This paper reports the effect of sintering temperature on ferroelectric properties of GdMnO3 (GMO) bulk ceramics at room temperature prepared by the conventional solid state reaction route following slow step sintering schedule. Ferroelectric hysteresis loop as well as sharp dielectric anomaly in pure (99.999%) GMO sintered ceramics has been clearly observed. Samples sintered at 1350 °C become orthorhombic with Pbnm space group and showed frequency independent sharp dielectric anomalies at 373 K and a square type of novel ferroelectric hysteresis loop was observed at room temperature. Interestingly, dielectric anomalies and ferroelectric behavior were observed to be dependent upon sintering temperature of GdMnO3. Room temperature dielectric constant (ɛr) value at different frequencies is observed to be abnormally high. The magnetic field and temperature dependent magnetization show antiferromagnetic behavior at 40 K for both 1350 °C and 1700 °C sintered GMO. Present findings showed the possibility of application of GdMnO3 at room temperature as multifunctional materials.

Cardiac transient outward potassium current: a pulse chemistry model of frequency-dependent properties.

PubMed

Liu, L; Krinsky, V I; Grant, A O; Starmer, C F

1996-01-01

Recent voltage-clamp studies of isolated myocytes have demonstrated widespread occurrence of a transient outward current (I(to)) carried by potassium ions. In the canine ventricle, this current is well developed in epicardial cells but not in endocardial cells. The resultant spatial dispersion of refractoriness is potentially proarrhythmic and may be amplified by channel blockade. The inactivation and recovery time constants of this channel are in excess of several hundred milliseconds, and consequently channel availability is frequency dependent at physiological stimulation rates. When the time constants associated with transitions between different channel conformations are rapid relative to drug binding kinetics, the interactions between drugs and an ion channel can be approximated by a sequence of first-order reactions, in which binding occurs in pulses in response to pulse train stimulation (pulse chemistry). When channel conformation transition time constants do not meet this constraint, analytical characterizations of the drug-channel interaction must then be modified to reflect the channel time-dependent properties. Here we report that the rate and steady-state amount of frequency-dependent inactivation of I(to) are consistent with a generalization of the channel blockade model: channel availability is reduced in a pulsatile exponential pattern as the stimulation frequency is increased, and the rate of reduction is a linear function of the pulse train depolarizing and recovery intervals. I(to) was reduced in the presence of quinidine. After accounting for the use-dependent availability of I(to) channels, we found little evidence of an additional use-dependent component of block after exposure to quinidine, suggesting that quinidine reacts with both open and closed I(to) channels as though the binding site is continuously accessible. The model provides a useful tool for assessing drug-channel interactions when the reaction cannot be continuously monitored.

Phonon-drag magnetothermopower in Rashba spin-split two-dimensional electron systems.

PubMed

Biswas, Tutul; Ghosh, Tarun Kanti

2013-10-16

We study the phonon-drag contribution to the thermoelectric power in a quasi-two-dimensional electron system confined in GaAs/AlGaAs heterostructure in the presence of both Rashba spin-orbit interaction and perpendicular magnetic field at very low temperature. It is observed that the peaks in the phonon-drag thermopower split into two when the Rashba spin-orbit coupling constant is strong. This splitting is a direct consequence of the Rashba spin-orbit interaction. We show the dependence of phonon-drag thermopower on both magnetic field and temperature numerically. A power-law dependence of phonon-drag magnetothermopower on the temperature in the Bloch-Gruneisen regime is found. We also extract the exponent of the temperature dependence of phonon-drag thermopower for different parameters like electron density, magnetic field, and the spin-orbit coupling constant.

On the period of the periodic orbits of the restricted three body problem

NASA Astrophysics Data System (ADS)

Perdomo, Oscar

2017-09-01

We will show that the period T of a closed orbit of the planar circular restricted three body problem (viewed on rotating coordinates) depends on the region it encloses. Roughly speaking, we show that, 2 T=kπ +\\int _Ω g where k is an integer, Ω is the region enclosed by the periodic orbit and g:R^2→ R is a function that only depends on the constant C known as the Jacobian constant; it does not depend on Ω . This theorem has a Keplerian flavor in the sense that it relates the period with the space "swept" by the orbit. As an application we prove that there is a neighborhood around L_4 such that every periodic solution contained in this neighborhood must move clockwise. The same result holds true for L_5.

Temperature dependence of electrical characteristics of Pt/GaN Schottky diode fabricated by UHV e-beam evaporation.

PubMed

Kumar, Ashish; Arafin, Shamsul; Amann, Markus Christian; Singh, Rajendra

2013-11-15

Temperature-dependent electrical characterization of Pt/n-GaN Schottky barrier diodes prepared by ultra high vacuum evaporation has been done. Analysis has been made to determine the origin of the anomalous temperature dependence of the Schottky barrier height, the ideality factor, and the Richardson constant calculated from the I-V-T characteristics. Variable-temperature Hall effect measurements have been carried out to understand charge transport at low temperature. The modified activation energy plot from the barrier inhomogeneity model has given the value of 32.2 A/(cm2 K2) for the Richardson constant A** in the temperature range 200 to 380 K which is close to the known value of 26.4A/(cm2 K2) for n-type GaN.

Calculated temperature dependence of elastic constants and phonon dispersion of hcp and bcc beryllium

NASA Astrophysics Data System (ADS)

Hahn, Steven; Arapan, Sergiu; Harmon, Bruce; Eriksson, Olle

2011-03-01

Conventional first principle methods for calculating lattice dynamics are unable to calculate high temperature thermophysical properties of materials containing modes that are entropically stabilized. In this presentation we use a relatively new approach called self-consistent ab initio lattice dynamics (SCAILD) to study the hcp to bcc transition (1530 K) in beryllium. The SCAILD method goes beyond the harmonic approximation to include phonon-phonon interactions and produces a temperature-dependent phonon dispersion. In the high temperature bcc structure, phonon-phonon interactions dynamically stabilize the N-point phonon. Fits to the calculated phonon dispersion were used to determine the temperature dependence of the elastic constants in the hcp and bcc phases. Work at the Ames Laboratory was supported by the Department of Energy-Basic Energy Sciences under Contract No. DE-AC02-07CH11358.

Teaching Chemical Equilibrium with the Jigsaw Technique

NASA Astrophysics Data System (ADS)

Doymus, Kemal

2008-03-01

This study investigates the effect of cooperative learning (jigsaw) versus individual learning methods on students’ understanding of chemical equilibrium in a first-year general chemistry course. This study was carried out in two different classes in the department of primary science education during the 2005-2006 academic year. One of the classes was randomly assigned as the non-jigsaw group (control) and other as the jigsaw group (cooperative). Students participating in the jigsaw group were divided into four “home groups” since the topic chemical equilibrium is divided into four subtopics (Modules A, B, C and D). Each of these home groups contained four students. The groups were as follows: (1) Home Group A (HGA), representin g the equilibrium state and quantitative aspects of equilibrium (Module A), (2) Home Group B (HGB), representing the equilibrium constant and relationships involving equilibrium constants (Module B), (3) Home Group C (HGC), representing Altering Equilibrium Conditions: Le Chatelier’s principle (Module C), and (4) Home Group D (HGD), representing calculations with equilibrium constants (Module D). The home groups then broke apart, like pieces of a jigsaw puzzle, and the students moved into jigsaw groups consisting of members from the other home groups who were assigned the same portion of the material. The jigsaw groups were then in charge of teaching their specific subtopic to the rest of the students in their learning group. The main data collection tool was a Chemical Equilibrium Achievement Test (CEAT), which was applied to both the jigsaw and non-jigsaw groups The results indicated that the jigsaw group was more successful than the non-jigsaw group (individual learning method).

On the origin of size-dependent and size-independent crystal growth: Influence of advection and diffusion

USGS Publications Warehouse

Kile, D.E.; Eberl, D.D.

2003-01-01

Crystal growth experiments were conducted using potassium alum and calcite crystals in aqueous solution under both non-stirred and stirred conditions to elucidate the mechanism for size-dependent (proportionate) and size-independent (constant) crystal growth. Growth by these two laws can be distinguished from each other because the relative size difference among crystals is maintained during proportionate growth, leading to a constant crystal size variance (??2) for a crystal size distribution (CSD) as the mean size increases. The absolute size difference among crystals is maintained during constant growth, resulting in a decrease in size variance. Results of these experiments show that for centimeter-sized alum crystals, proportionate growth occurs in stirred systems, whereas constant growth occurs in non-stirred systems. Accordingly, the mechanism for proportionate growth is hypothesized to be related to the supply of reactants to the crystal surface by advection, whereas constant growth is related to supply by diffusion. Paradoxically, micrometer-sized calcite crystals showed proportionate growth both in stirred and in non-stirred systems. Such growth presumably results from the effects of convection and Brownian motion, which promote an advective environment and hence proportionate growth for minute crystals in non-stirred systems, thereby indicating the importance of solution velocity relative to crystal size. Calcite crystals grown in gels, where fluid motion was minimized, showed evidence for constant, diffusion-controlled growth. Additional investigations of CSDs of naturally occurring crystals indicate that proportionate growth is by far the most common growth law, thereby suggesting that advection, rather than diffusion, is the dominant process for supplying reactants to crystal surfaces.

Turbulent flows over superhydrophobic surfaces with shear-dependent slip length

NASA Astrophysics Data System (ADS)

Khosh Aghdam, Sohrab; Seddighi, Mehdi; Ricco, Pierre

2015-11-01

Motivated by recent experimental evidence, shear-dependent slip length superhydrophobic surfaces are studied. Lyapunov stability analysis is applied in a 3D turbulent channel flow and extended to the shear-dependent slip-length case. The feedback law extracted is recognized for the first time to coincide with the constant-slip-length model widely used in simulations of hydrophobic surfaces. The condition for the slip parameters is found to be consistent with the experimental data and with values from DNS. The theoretical approach by Fukagata (PoF 18.5: 051703) is employed to model the drag-reduction effect engendered by the shear-dependent slip-length surfaces. The estimated drag-reduction values are in very good agreement with our DNS data. For slip parameters and flow conditions which are potentially realizable in the lab, the maximum computed drag reduction reaches 50%. The power spent by the turbulent flow on the walls is computed, thereby recognizing the hydrophobic surfaces as a passive-absorbing drag-reduction method, as opposed to geometrically-modifying techniques that do not consume energy, e.g. riblets, hence named passive-neutral. The flow is investigated by visualizations, statistical analysis of vorticity and strain rates, and quadrants of the Reynolds stresses. Part of this work was funded by Airbus Group. Simulations were performed on the ARCHER Supercomputer (UKTC Grant).

Theory of the milieu dependent isomerisation dynamics of reducing sugars applied to d-erythrose.

PubMed

Kaufmann, Martin; Mügge, Clemens; Kroh, Lothar W

2015-12-11

Quantitative (1)H selective saturation transfer NMR spectroscopy ((1)H SST qNMR) was used to fully describe the milieu dependent dynamics of the isomeric system of d-erythrose. Thermodynamic activation parameters are calculated for acidic as well as for basic catalysis combining McConnell's modified Bloch equations for the chemical exchange solved for the constraint of saturating the non-hydrated acyclic isomer, the Eyring equation and Hudson's equation for pH dependent catalysis. A detailed mathematical examination describing the milieu dependent dynamics of sugar isomerisation is provided. Thermodynamic data show evidence that photo-catalysed sugar isomerisation as well as degradation has to be considered. Approximations describing the pH and temperature dependence of thermodynamic activation parameters are derived that indicate the possibility of photo-affecting equilibrium constants. Moreover, the results show that isomerisation dynamics are closely related to degradation kinetics and that sugars' reactivities are altered by the concentration of acyclic carbonyl isomer and the sum of its ring closing rate constants. Additionally, it is concluded that sugar solutions show a limited self-stabilising behaviour. Copyright © 2015 Elsevier Ltd. All rights reserved.

Temperature dependence of ion transport: the compensated Arrhenius equation.

PubMed

Petrowsky, Matt; Frech, Roger

2009-04-30

The temperature-dependent conductivity originating in a thermally activated process is often described by a simple Arrhenius expression. However, this expression provides a poor description of the data for organic liquid electrolytes and amorphous polymer electrolytes. Here, we write the temperature dependence of the conductivity as an Arrhenius expression and show that the experimentally observed non-Arrhenius behavior is due to the temperature dependence of the dielectric constant contained in the exponential prefactor. Scaling the experimentally measured conductivities to conductivities at a chosen reference temperature leads to a "compensated" Arrhenius equation that provides an excellent description of temperature-dependent conductivities. A plot of the prefactors as a function of the solvent dielectric constant results in a single master curve for each family of solvents. These data suggest that ion transport in these and related systems is governed by a single activated process differing only in the activation energy for each family of solvents. Connection is made to the shift factor used to describe electrical and mechanical relaxation in a wide range of phenomena, suggesting that this scaling procedure might have broad applications.

[Case control study on the treatment of acromioclavicular dislocation with Endobutton plates combined with an anchor].

PubMed

Hu, Jin-Tao; Lu, Jian-Wei; Fu, Li-Feng

2016-09-25

To compare the clinical effect of Endobutton plates combined with an anchor and clavicle hook plate in the treatment of acromioclavicular dislocation. From January 2012 to August 2014, 83 patients with Rockwood type III acromioclavicular dislocation underwent surgical treatments. Among them, 34 patients were treated with Endobutton plate and anchor repair(Endobutton group), including 23 males and 11 females, and the mean age was(39.0±6.3) years old (26 to 51 years old); the average time from injury to operation was(4.1±1.3) days(3 to 7 days);the injured side:14 left, 20 right; the dislocation in 28 patients dues to fall, 6 patients dues traffic accident. There were 49 patients treated with clavicular hook plate(hook plate group), including 33 males and 16 females;the mean age was(37.9±6.3) years old (27 to 53 years old); the average time from injury to operation was(4.1±1.1) days (2 to 7 days);the injured side: 18 left, 31 right;the dislication in 36 patients dues to fall, 13 patients dues traffic accidents. The indexes such as intraoperative bleeding volume, operation time, incision size, postoperative complication and postoperative coracoclavicular space, shoulder joint function, and life quality were compared between two groups. In the hook plate group with 49 patients, the plates in 43 patients were removed at the secondary operation, and 32 patients had shoulder pain or limited active range. Thirty four patients in the Endobutton group had no pain symptoms and limited active range. All the patients did not suffer acromioclavicular dislocation again. There was no significant difference between the two groups in operation time, and intraoperative bleeding volume( P >0.05). The incision length in the hook plate group was longer than that in Endobutton group( P <0.05). The coracoclavicular space of the uninjured and injured side in two groups respectively had no significant differences, and the coracoclavicular space in the injured side between two group had no significant difference( P >0.05). There were no significant differences of Constant score and SF-36 between two groups 2 months after operation( P >0.05). Sixteen months after operation, the Constant score in the injured side of both groups was higher than that in 2 months postoperative. But the Constant score in the injured side of hook plate group was higher than that in Endobutton group( P <0.05). The Constant score in the uninjured side had no significant differences between two group( P >0.05). In hook plate group, the Constant score in the uninjured side was higher than that in the injured side. In Endobutton group, there were no significant differences of Constant score between two sides. The 16 month postoperative SF-36 in the injured side of both groups was higher than the 2 month postoperative one, but 16 month postoperative SF-36 in hook plate group was lower than that in Endobutton group ( P <0.05). Endobutton plate combined with an anchor can effectively fix Rockwood type III or more acute acromioclavicular dislocation. The method has less complications, avoiding secondary removal of internal fixation.

Flexor and extensor muscle tone evaluated using the quantitative pendulum test in stroke and parkinsonian patients.

PubMed

Huang, Han-Wei; Ju, Ming-Shaung; Lin, Chou-Ching K

2016-05-01

The aim of this study was to evaluate the flexor and extensor muscle tone of the upper limbs in patients with spasticity or rigidity and to investigate the difference in hypertonia between spasticity and rigidity. The two experimental groups consisted of stroke patients and parkinsonian patients. The control group consisted of age and sex-matched normal subjects. Quantitative upper limb pendulum tests starting from both flexed and extended joint positions were conducted. System identification with a simple linear model was performed and model parameters were derived. The differences between the three groups and two starting positions were investigated by these model parameters and tested by two-way analysis of variance. In total, 57 subjects were recruited, including 22 controls, 14 stroke patients and 21 parkinsonian patients. While stiffness coefficient showed no difference among groups, the number of swings, relaxation index and damping coefficient showed changes suggesting significant hypertonia in the two patient groups. There was no difference between these two patient groups. The test starting from the extended position constantly manifested higher muscle tone in all three groups. In conclusion, the hypertonia of parkinsonian and stroke patients could not be differentiated by the modified pendulum test; the elbow extensors showed a higher muscle tone in both control and patient groups; and hypertonia of both parkinsonian and stroke patients is velocity dependent. Copyright © 2015 Elsevier Ltd. All rights reserved.

Ligands of low electronegativity in the vsepr model: molecular pseudohalides

NASA Astrophysics Data System (ADS)

Glidewell, Christopher; Holden, H. Diane

Equilibrium structures and force constants at linearity, for the skeletal bending mode δ(RNX) have been calculated in the MNDO approximation for 67 isocyanates, isothio-cyanates and azides, RNXY (XY = CO, CS or N 2) and the corresponding structures and force constants, δ(RCN), for 12 fulminates RCNO. Fulminates all have linear skeletons, but for RNXY the molecular skeleton is linear at atom X only if it is linear at N also ; otherwise the skeleton RNXY has a trans planar structure. Bending force constants are large and negative for all azides studied, negative for methyl and substituted methyl isocyanates and isothiocyanates and very small and positive for silyl and substituted silyl isothiocyanates: for silyl and substituted silyl isocyanales, the force constant is small and positive when the R group has effective C2v symmetry, but small and negative when the R group has only effective Cs symmetry.

Single-scale renormalisation group improvement of multi-scale effective potentials

NASA Astrophysics Data System (ADS)

Chataignier, Leonardo; Prokopec, Tomislav; Schmidt, Michael G.; Świeżewska, Bogumiła

2018-03-01

We present a new method for renormalisation group improvement of the effective potential of a quantum field theory with an arbitrary number of scalar fields. The method amounts to solving the renormalisation group equation for the effective potential with the boundary conditions chosen on the hypersurface where quantum corrections vanish. This hypersurface is defined through a suitable choice of a field-dependent value for the renormalisation scale. The method can be applied to any order in perturbation theory and it is a generalisation of the standard procedure valid for the one-field case. In our method, however, the choice of the renormalisation scale does not eliminate individual logarithmic terms but rather the entire loop corrections to the effective potential. It allows us to evaluate the improved effective potential for arbitrary values of the scalar fields using the tree-level potential with running coupling constants as long as they remain perturbative. This opens the possibility of studying various applications which require an analysis of multi-field effective potentials across different energy scales. In particular, the issue of stability of the scalar potential can be easily studied beyond tree level.

Rationale choosing interval of a piecewise-constant approximation of input rate of non-stationary queue system

NASA Astrophysics Data System (ADS)

Korelin, Ivan A.; Porshnev, Sergey V.

2018-01-01

The paper demonstrates the possibility of calculating the characteristics of the flow of visitors to objects carrying out mass events passing through checkpoints. The mathematical model is based on the non-stationary queuing system (NQS) where dependence of requests input rate from time is described by the function. This function was chosen in such way that its properties were similar to the real dependencies of speed of visitors arrival on football matches to the stadium. A piecewise-constant approximation of the function is used when statistical modeling of NQS performing. Authors calculated the dependencies of the queue length and waiting time for visitors to service (time in queue) on time for different laws. Time required to service the entire queue and the number of visitors entering the stadium at the beginning of the match were calculated too. We found the dependence for macroscopic quantitative characteristics of NQS from the number of averaging sections of the input rate.

State dependent model predictive control for orbital rendezvous using pulse-width pulse-frequency modulated thrusters

NASA Astrophysics Data System (ADS)

Li, Peng; Zhu, Zheng H.; Meguid, S. A.

2016-07-01

This paper studies the pulse-width pulse-frequency modulation based trajectory planning for orbital rendezvous and proximity maneuvering near a non-cooperative spacecraft in an elliptical orbit. The problem is formulated by converting the continuous control input, output from the state dependent model predictive control, into a sequence of pulses of constant magnitude by controlling firing frequency and duration of constant-magnitude thrusters. The state dependent model predictive control is derived by minimizing the control error of states and control roughness of control input for a safe, smooth and fuel efficient approaching trajectory. The resulting nonlinear programming problem is converted into a series of quadratic programming problem and solved by numerical iteration using the receding horizon strategy. The numerical results show that the proposed state dependent model predictive control with the pulse-width pulse-frequency modulation is able to effectively generate optimized trajectories using equivalent control pulses for the proximity maneuvering with less energy consumption.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wiedemeier, Heribert, E-mail: wiedeh@rpi.ed

Correlations of computed Schottky constants (K{sub S}=[V''{sub Zn}][V{sub S}{sup ..}]) with structural and thermodynamic properties showed linear dependences of log K{sub S} on the lattice energies for the Zn-, Cd-, Hg-, Mg-, and Sr-chalcogenides and for the Na- and K-halides. These findings suggest a basic relation between the Schottky constants and the lattice energies for these families of compounds from different parts of the Periodic Table, namely, {Delta}H{sub T,L}{sup o}=-(2.303nRT log K{sub S})+2.303nRm{sub b}+2.303nRTi{sub b}. {Delta}H{sub T,L}{sup o} is the experimental (Born-Haber) lattice energy (enthalpy), n is a constant approximately equal to the formal valence (charge) of the material, m{submore » b} and i{sub b} are the slope and intercept, respectively, of the intercept b (of the log K{sub S} versus {Delta}H{sub L}{sup o} linear relation) versus the reciprocal temperature. The results of this work also provide an empirical correlation between the Gibbs free energy of vacancy formation and the lattice energy. - Graphical abstract: For the Zn-chalcogenides, the quantities n and I{sub e} are 2.007 and 650.3 kcal (2722 kJ), respectively. For the other groups of compounds, they are approximately equal to the formal valences and ionization energies of the metals: Log K{sub S{approx}}-(2.303nRT){sup -1} (0.99{Delta}H{sup o}{sub T,L}-I{sub e}).« less

Integral sliding mode-based attitude coordinated tracking for spacecraft formation with communication delays

NASA Astrophysics Data System (ADS)

Zhang, Jian; Hu, Qinglei; Xie, Wenbo

2017-11-01

This paper investigates the attitude coordinated tracking control for a group of rigid spacecraft under directed communication topology, in which inertia uncertainties, external disturbances, input saturation and constant time-delays between the formation members are handled. Initially, the nominal system with communication delays is studied. A delay-dependent controller is proposed by using Lyapunov-Krasovskii function and sufficient condition for system stability is derived. Then, an integral sliding manifold is designed and adaptive control approach is employed to deal with the total perturbation. Meanwhile, the boundary layer method is introduced to alleviate the unexpected chattering as system trajectories cross the switching surface. Finally, numerical simulation results are presented to validate the effectiveness and robustness of the proposed control strategy.

Action mechanism of tyrosinase on meta- and para-hydroxylated monophenols.

PubMed

Fenoll, L G; Rodríguez-López, J N; Varón, R; García-Ruiz, P A; García-Cánovas, F; Tudela, J

2000-04-01

The relationship between the structure and activity of meta- and para-hydroxylated monophenols was studied during their tyrosinase-catalysed hydroxylation and the rate-limiting steps of the reaction mechanism were identified. The para-hydroxylated substrates permit us to study the effect of a substituent (R) in the carbon-1 position (C-1) of the benzene ring on the nucleophilic attack step, while the meta group permits a similar study of the effect on the electrophilic attack step. Substrates with a -OCH3 group on C-1, as p-hydroxyanisol (4HA) and m-hydroxyanisol (3HA), or with a -CH2OH group, as p-hydroxybenzylalcohol (4HBA) and m-hydroxybenzylalcohol (3HBA), were used because the effect of the substituent (R) size was assumed to be similar. However, the electron-donating effect of the -OCH3 group means that the carbon-4 position (C-4) is favoured for nucleophilic attack (para-hydroxylated substrates) or for electrophilic attack (meta-hydroxylated substrates). The electron-attracting effect of the -CH2OH group has the opposite effect, hindering nucleophilic (para) or electrophilic (meta) attack of C-4. The experimental data point to differences between the maximum steady-state rate (V(M)Max) of the different substrates, the value of this parameter depends on the nucleophilic and electrophilic attack. However, differences are greatest in the Michaelis constants (K(M)m), with the meta-hydroxylated substrates having very large values. The catalytic efficiency k(M)cat/K(M)m is much greater for thepara-hydroxylated substrates although it varies greatly between one substrate and the other. However, it varies much less in the meta-hydroxylated substrates since this parameter describes the power of the nucleophilic attack, which is weaker in the meta OH. The large increase in the K(M)m of the meta-hydroxylated substrates might suggest that the phenolic OH takes part in substrate binding. Since this is a weaker nucleophil than the para-hydroxylated substrates, the binding constant decreases, leading to an increase in K(M)m. The catalytic efficiency of tyrosinase on a monophenol (para or meta) is directly related to the nucleophilic power of the oxygen of the phenolic OH. The oxidation step is not limiting since if this were the case, the para and meta substrates would have the same V(M)max. The small difference between the absolute values of V(M)max suggests that the rate constants of the nucleophilic and electrophilic attacks are on the same order of magnitude.

Entanglement entropy for (3+1)-dimensional topological order with excitations

NASA Astrophysics Data System (ADS)

Wen, Xueda; He, Huan; Tiwari, Apoorv; Zheng, Yunqin; Ye, Peng

2018-02-01

Excitations in (3+1)-dimensional [(3+1)D] topologically ordered phases have very rich structures. (3+1)D topological phases support both pointlike and stringlike excitations, and in particular the loop (closed string) excitations may admit knotted and linked structures. In this work, we ask the following question: How do different types of topological excitations contribute to the entanglement entropy or, alternatively, can we use the entanglement entropy to detect the structure of excitations, and further obtain the information of the underlying topological order? We are mainly interested in (3+1)D topological order that can be realized in Dijkgraaf-Witten (DW) gauge theories, which are labeled by a finite group G and its group 4-cocycle ω ∈H4[G ;U(1 ) ] up to group automorphisms. We find that each topological excitation contributes a universal constant lndi to the entanglement entropy, where di is the quantum dimension that depends on both the structure of the excitation and the data (G ,ω ) . The entanglement entropy of the excitations of the linked/unlinked topology can capture different information of the DW theory (G ,ω ) . In particular, the entanglement entropy introduced by Hopf-link loop excitations can distinguish certain group 4-cocycles ω from the others.

Growth, structural, spectroscopic and optical characterization of barium doped calcium tartrate

NASA Astrophysics Data System (ADS)

Verma, Seema; Raina, Bindu; Gupta, Vandana; Bamzai, K. K.

2018-05-01

Barium doped calcium tartrates synthesized by controlled diffusion using silica gel technique at ambient temperature was characterized by single crystal X-ray diffraction which establishes monoclinic crystal system with volume of the unit cell 923.97(10) Ǻ3 and the space group being P21. UV - Vis characterization gives various linear optical constants like absorption, transmittance, reflectance, band gap, extinction coefficient, urbach energy, complex dielectric constant, optical and electrical conductivity. These constants are considered to be essential in characterizing materials that are used in various applications like fabrication of optoelectronic devices. FTIR spectrum establishes the presence of various bands of functional groups expected from metal tartrate with water of crystallization.

Partial compilation and revision of basic data in the WATEQ programs

USGS Publications Warehouse

Nordstrom, D. Kirk; Valentine, S.D.; Ball, J.W.; Plummer, Niel; Jones, B.F.

1984-01-01

Several portions of the basic data in the WATEQ series of computer programs (WATEQ, WATEQF, WATEQ2, WATEQ3, and PHREEQE) are compiled. The density and dielectric constant of water and their temperature dependence are evaluated for the purpose of updating the Debye-Huckel solvent parameters in the activity coefficient equations. The standard state thermodynamic properties of the Fe2+ and Fe3+ aqueous ions are refined. The main portion of this report is a comprehensive listing of aluminum hydrolysis constants, aluminum fluoride, aluminum sulfate, calcium chloride, magnesium chloride, potassium sulfate and sodium sulfate stability constants, solubility product constants for gibbsite and amorphous aluminum hydroxide, and the standard electrode potentials for Fe (s)/Fe2+(aq) and Fe2 +(aq)/Fe3+(aq). (USGS)

Instanton rate constant calculations close to and above the crossover temperature.

PubMed

McConnell, Sean; Kästner, Johannes

2017-11-15

Canonical instanton theory is known to overestimate the rate constant close to a system-dependent crossover temperature and is inapplicable above that temperature. We compare the accuracy of the reaction rate constants calculated using recent semi-classical rate expressions to those from canonical instanton theory. We show that rate constants calculated purely from solving the stability matrix for the action in degrees of freedom orthogonal to the instanton path is not applicable at arbitrarily low temperatures and use two methods to overcome this. Furthermore, as a by-product of the developed methods, we derive a simple correction to canonical instanton theory that can alleviate this known overestimation of rate constants close to the crossover temperature. The combined methods accurately reproduce the rate constants of the canonical theory along the whole temperature range without the spurious overestimation near the crossover temperature. We calculate and compare rate constants on three different reactions: H in the Müller-Brown potential, methylhydroxycarbene → acetaldehyde and H 2  + OH → H + H 2 O. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Kinetic intermediates of unfolding of dimeric prostatic phosphatase.

PubMed

Kuciel, Radosława; Mazurkiewicz, Aleksandra; Dudzik, Paulina

2007-01-01

Kinetics of guanidine hydrochloride (GdnHCl)-induced unfolding of human prostatic acid phosphatase (hPAP), a homodimer of 50 kDa subunit molecular mass was investigated with enzyme activity measurements, capacity for binding an external hydrophobic probe, 1-anilinonaphtalene-8-sulfonate (ANS), accessibility of thiols to reaction with 5,5'-dithiobis(2-nitrobenzoic acid) (DTNB) and 2-(4'-maleimidylanilino)naphthalene-6-sulfonate (MIANS) and ability to bind Congo red dye. Kinetic analysis was performed to describe a possible mechanism of hPAP unfolding and dissociation that leads to generation of an inactive monomeric intermediate that resembles, in solution of 1.25 M GdnHCl pH 7.5, at 20 degrees C, in equilibrium, a molten globule state. The reaction of hPAP inactivation in 1.25 M GdnHCl followed first order kinetics with the reaction rate constant 0.0715 +/- 0.0024 min(-1) . The rate constants of similar range were found for the pseudo-first-order reactions of ANS and Congo red binding: 0.0366 +/- 0.0018 min(-1) and 0.0409 +/- 0.0052 min(-1), respectively. Free thiol groups, inaccessible in the native protein, were gradually becoming, with the progress of unfolding, exposed for the reactions with DTNB and MIANS, with the pseudo-first-order reaction rate constants 0.327 +/- 0.014 min(-1) and 0.216 +/- 0.010 min(-1), respectively. The data indicated that in the course of hPAP denaturation exposure of thiol groups to reagents took place faster than the enzyme inactivation and exposure of the protein hydrophobic surface. This suggested the existence of a catalytically active, partially unfolded, but probably dimeric kinetic intermediate in the process of hPAP unfolding. On the other hand, the protein inactivation was accompanied by exposure of a hydrophobic, ANS-binding surface, and with an increased capacity to bind Congo red. Together with previous studies these results suggest that the stability of the catalytically active conformation of the enzyme depends mainly on the dimeric structure of the native hPAP.

Self-diffusion in a system of interacting Langevin particles

NASA Astrophysics Data System (ADS)

Dean, D. S.; Lefèvre, A.

2004-06-01

The behavior of the self-diffusion constant of Langevin particles interacting via a pairwise interaction is considered. The diffusion constant is calculated approximately within a perturbation theory in the potential strength about the bare diffusion constant. It is shown how this expansion leads to a systematic double expansion in the inverse temperature β and the particle density ρ . The one-loop diagrams in this expansion can be summed exactly and we show that this result is exact in the limit of small β and ρβ constants. The one-loop result can also be resummed using a semiphenomenological renormalization group method which has proved useful in the study of diffusion in random media. In certain cases the renormalization group calculation predicts the existence of a diverging relaxation time signaled by the vanishing of the diffusion constant, possible forms of divergence coming from this approximation are discussed. Finally, at a more quantitative level, the results are compared with numerical simulations, in two dimensions, of particles interacting via a soft potential recently used to model the interaction between coiled polymers.

Evidence of preorganization in quinonoid intermediate formation from L-Trp in H463F mutant Escherichia coli tryptophan indole-lyase from effects of pressure and pH.

PubMed

Phillips, Robert S; Kalu, Ukoha; Hay, Sam

2012-08-21

The effects of pH and hydrostatic pressure on the reaction of H463F tryptophan indole-lyase (TIL) have been evaluated. The mutant TIL shows very low activity for elimination of indole but is still competent to form a quinonoid intermediate from l-tryptophan [Phillips, R. S., Johnson, N., and Kamath, A. V. (2002) Biochemistry 41, 4012-4019]. Stopped-flow measurements show that the formation of the quinonoid intermediate at 505 nm is affected by pH, with a bell-shaped dependence for the forward rate constant, k(f), and dependence on a single basic group for the reverse rate constant, k(r), with the following values: pK(a1) = 8.14 ± 0.15, pK(a2) = 7.54 ± 0.15, k(f,min) = 18.1 ± 1.3 s(-1), k(f,max) = 179 ± 46.3 s(-1), k(r,min) = 11.4 ± 1.2 s(-1), and k(r,max) = 33 ± 1.6 s(-1). The pH effects may be due to ionization of Tyr74 as the base and Cys298 as the acid influencing the rate constant for deprotonation. High-pressure stopped-flow measurements were performed at pH 8, which is the optimum for the forward reaction. The rate constants show an increase with pressure up to 100 MPa and a subsequent decrease above 100 MPa. Fitting the pressure data gives the following values: k(f,0) = 15.4 ± 0.8 s(-1), ΔV(‡) = -29.4 ± 2.9 cm(3) mol(-1), and Δβ(‡) = -0.23 ± 0.03 cm(3) mol(-1) MPa(-1) for the forward reaction, and k(r,0) = 20.7 ± 0.8 s(-1), ΔV(‡) = -9.6 ± 2.3 cm(3) mol(-1), and Δβ(‡) = -0.05 ± 0.02 cm(3) mol(-1) MPa(-1) for the reverse reaction. The primary kinetic isotope effect on quinonoid intermediate formation at pH 8 is small (~2) and is not significantly pressure-dependent, suggesting that the effect of pressure on k(f) may be due to perturbation of an active site preorganization step. The negative activation volume is also consistent with preorganization of the ES complex prior to quinonoid intermediate formation, and the negative compressibility may be due to the effect of pressure on the enzyme conformation. These results support the conclusion that the preorganization of the H463F TIL Trp complex, which is probably dominated by motion of the l-Trp indole moiety of the aldimine complex, contributes to quinonoid intermediate formation.

Dielectric constants of soils at microwave frequencies-2

NASA Technical Reports Server (NTRS)

Wang, J.; Schmugge, T.; Williams, D.

1978-01-01

The dielectric constants of several soil samples were measured at frequencies of 5 and 19 GHz using the infinite transmission line method. The results of these measurements are presented and discussed with respect to soil types and texture structures. A comparison is made with other measurements at 1.4 GHz. At all three frequencies, the dependence of dielectric constant on soil moisture can be approximated by two straight lines. At low moisture, the slope is less than at high moisture level. The intersection of the two lines is believed to be a function of soil texture.

Newman-Penrose constants of the Kerr-Newman metric

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gong Xuefei; Shang Yu; Bai Shan

The Newman-Unti formalism of the Kerr-Newman metric near future null infinity is developed, with which the Newman-Penrose constants for both the gravitational and electromagnetic fields of the Kerr-Newman metric are computed and shown to be zero. The multipole structure near future null infinity in the sense of Janis-Newman of the Kerr-Newman metric is then further studied. It is found that up to the 2{sup 4}-pole, modulo a constant dependent upon the order of the pole, these multipole moments agree with those of Geroch-Hansen multipole moments defined at spatial infinity.

1,2-Difluoroethane: the angular dependance on 1J(CF) coupling constants is independent of hyperconjugation.

PubMed

Freitas, Matheus P; Bühl, Michael; O'Hagan, David

2012-02-28

1,2-Difluoroethane is widely recognised to adopt a lower energy gauche rather than anti conformation; this gauche effect has its origin in hyperconjugation; however, surprisingly the (1)J(CF) coupling constant is not influenced by hyperconjugation; instead, its magnitude changes with the overall molecular dipole. This journal is © The Royal Society of Chemistry 2012

An equivalent dipole analysis of PZT ceramics and lead-free piezoelectric single crystals

NASA Astrophysics Data System (ADS)

Bell, Andrew J.

2016-04-01

The recently proposed Equivalent Dipole Model for describing the electromechanical properties of ionic solids in terms of 3 ions and 2 bonds has been applied to PZT ceramics and lead-free single crystal piezoelectric materials, providing analysis in terms of an effective ionic charge and the asymmetry of the interatomic force constants. For PZT it is shown that, as a function of composition across the morphotropic phase boundary, the dominant bond compliance peaks at 52% ZrO2. The stiffer of the two bonds shows little composition dependence with no anomaly at the phase boundary. The effective charge has a maximum value at 50% ZrO2, decreasing across the phase boundary region, but becoming constant in the rhombohedral phase. The single crystals confirm that both the asymmetry in the force constants and the magnitude of effective charge are equally important in determining the values of the piezoelectric charge coefficient and the electromechanical coupling coefficient. Both are apparently temperature dependent, increasing markedly on approaching the Curie temperature.

Latitude dependence of solar wind velocity observed at not less than 1 AU

NASA Technical Reports Server (NTRS)

Mitchell, D. G.; Roelof, E. C.; Wolfe, J. H.

1981-01-01

The large-scale solar wind velocity structure in the outer heliosphere has been systematically analyzed for Carrington rotations 1587-1541 (March 1972 to April 1976). Spacecraft data were taken from Imp 7/8 at earth, Pioneer 6, 8, and 9 near 1 AU, and Pioneer 10 and 11 between 1.6 and 5 AU. Using the constant radial velocity solar wind approximation to map all of the velocity data to its high coronal emission heliolongitude, the velocity structure observed at different spacecraft was examined for latitudinal dependence and compared with coronal structure in soft X-rays and H-alpha absorption features. The constant radial velocity approximation usually remains self-consistent in decreasing or constant velocity solar wind out to 5 AU, enabling us to separate radial from latitudinal propagation effects. Several examples of sharp nonmeridional stream boundaries in interplanetary space (about 5 deg latitude in width), often directly associated with features in coronal X-rays and H-alpha were found.

Atomistic simulation of CO2 solubility in poly(ethylene oxide) oligomers

NASA Astrophysics Data System (ADS)

Hong, Bingbing; Panagiotopoulos, Athanassios Z.

2014-06-01

We have performed atomistic molecular dynamics simulations coupled with thermodynamic integration to obtain the excess chemical potential and pressure-composition phase diagrams for CO2 in poly(ethylene oxide) oligomers. Poly(ethylene oxide) dimethyl ether, CH3O(CH2CH2O)nCH3 (PEO for short) is a widely applied physical solvent that forms the major organic constituent of a class of novel nanoparticle-based absorbents. Good predictions were obtained for pressure-composition-density relations for CO2 + PEO oligomers (2 ≤ n ≤ 12), using the Potoff force field for PEO [J. Chem. Phys. 136, 044514 (2012)] together with the TraPPE model for CO2 [AIChE J. 47, 1676 (2001)]. Water effects on Henry's constant of CO2 in PEO have also been investigated. Addition of modest amounts of water in PEO produces a relatively small increase in Henry's constant. Dependence of the calculated Henry's constant on the weight percentage of water falls on a temperature-dependent master curve, irrespective of PEO chain length.

Electrical detection of ortho–para conversion in fullerene-encapsulated water

PubMed Central

Meier, Benno; Mamone, Salvatore; Concistrè, Maria; Alonso-Valdesueiro, Javier; Krachmalnicoff, Andrea; Whitby, Richard J.; Levitt, Malcolm H.

2015-01-01

Water exists in two spin isomers, ortho and para, that have different nuclear spin states. In bulk water, rapid proton exchange and hindered molecular rotation obscure the direct observation of two spin isomers. The supramolecular endofullerene H2O@C60 provides freely rotating, isolated water molecules even at cryogenic temperatures. Here we show that the bulk dielectric constant of this substance depends on the ortho/para ratio, and changes slowly in time after a sudden temperature jump, due to nuclear spin conversion. The attribution of the effect to ortho–para conversion is validated by comparison with nuclear magnetic resonance and quantum theory. The change in dielectric constant is consistent with an electric dipole moment of 0.51±0.05 Debye for an encapsulated water molecule, indicating the partial shielding of the water dipole by the encapsulating cage. The dependence of bulk dielectric constant on nuclear spin isomer composition appears to be a previously unreported physical phenomenon. PMID:26299447

Geometrical feature of the scaling behavior of the limit-point pressure of inflated hyperelastic membranes.

PubMed

Tamadapu, Ganesh; Dhavale, Nikhil Nandkumar; DasGupta, Anirvan

2013-11-01

The occurrence of the limit-point instability is an intriguing phenomenon observed during stretching of hyperelastic membranes. In toy rubber balloons, this phenomenon may be experienced in the sudden reduction in the level of difficulty of blowing the balloon accompanied by its rapid inflation. The present paper brings out a link between the geometry and strain-hardening parameter of the membrane, and the occurrence of the limit-point instability. Inflation of membranes with different geometries and boundary conditions is considered, and the corresponding limit-point pressures are obtained for different strain-hardening parameter values. Interestingly, it is observed that the limit-point pressure for the different geometries is inversely proportional to a geometric parameter of the uninflated membrane. This dependence is shown analytically, which can be extended to a general membrane geometry. More surprisingly, the proportionality constant has a power-law dependence on the nondimensional material strain-hardening parameter. The constants involved in the power-law relation are universal constants for a particular membrane geometry.

Pressure and temperature dependences of the reaction of OH with nitric acid

NASA Technical Reports Server (NTRS)

Stachnik, R. A.; Molina, L. T.; Molina, M. J.

1986-01-01

Rate constants for the reaction of OH with HNO3 have been measured by using a laser flash photolysis resonance absorption technique at 298 and 248 K in the presence of 10-730 Torr of He, N2, and SF6. A dependence on total pressure was observed with rate constant values increasing at 298 K from 1.11 x 10 to the -13th cu cm/molecule/s at 10 Torr to 1.45 x 10 to the -13th cu cm/molecule/s at 730 Torr, and at 248 K from 1.87 x 10 to the -13th cu cm/molecule/s at 10 Torr to 3.07 x 10 to the -13th cu cm/molecule/s at 730 Torr with helium as the diluent gas. Falloff behavior occurred at lower pressures with SF6 or N2 as the diluent gas. Extrapolated zero pressure rate constants were determined and correspond to an Arrhenius activation energy of E/R = -710 K.

Galaxy Formation Efficiency and the Multiverse Explanation of the Cosmological Constant with EAGLE Simulations

NASA Astrophysics Data System (ADS)

Barnes, Luke A.; Elahi, Pascal J.; Salcido, Jaime; Bower, Richard G.; Lewis, Geraint F.; Theuns, Tom; Schaller, Matthieu; Crain, Robert A.; Schaye, Joop

2018-04-01

Models of the very early universe, including inflationary models, are argued to produce varying universe domains with different values of fundamental constants and cosmic parameters. Using the cosmological hydrodynamical simulation code from the EAGLE collaboration, we investigate the effect of the cosmological constant on the formation of galaxies and stars. We simulate universes with values of the cosmological constant ranging from Λ = 0 to Λ0 × 300, where Λ0 is the value of the cosmological constant in our Universe. Because the global star formation rate in our Universe peaks at t = 3.5 Gyr, before the onset of accelerating expansion, increases in Λ of even an order of magnitude have only a small effect on the star formation history and efficiency of the universe. We use our simulations to predict the observed value of the cosmological constant, given a measure of the multiverse. Whether the cosmological constant is successfully predicted depends crucially on the measure. The impact of the cosmological constant on the formation of structure in the universe does not seem to be a sharp enough function of Λ to explain its observed value alone.

Galaxy formation efficiency and the multiverse explanation of the cosmological constant with EAGLE simulations

NASA Astrophysics Data System (ADS)

Barnes, Luke A.; Elahi, Pascal J.; Salcido, Jaime; Bower, Richard G.; Lewis, Geraint F.; Theuns, Tom; Schaller, Matthieu; Crain, Robert A.; Schaye, Joop

2018-07-01

Models of the very early Universe, including inflationary models, are argued to produce varying universe domains with different values of fundamental constants and cosmic parameters. Using the cosmological hydrodynamical simulation code from the EAGLE collaboration, we investigate the effect of the cosmological constant on the formation of galaxies and stars. We simulate universes with values of the cosmological constant ranging from Λ = 0 to Λ0 × 300, where Λ0 is the value of the cosmological constant in our Universe. Because the global star formation rate in our Universe peaks at t = 3.5 Gyr, before the onset of accelerating expansion, increases in Λ of even an order of magnitude have only a small effect on the star formation history and efficiency of the universe. We use our simulations to predict the observed value of the cosmological constant, given a measure of the multiverse. Whether the cosmological constant is successfully predicted depends crucially on the measure. The impact of the cosmological constant on the formation of structure in the universe does not seem to be a sharp enough function of Λ to explain its observed value alone.

Steady-state kinetics of solitary batrachotoxin-treated sodium channels. Kinetics on a bounded continuum of polymer conformations.

PubMed Central

Rubinson, K A

1992-01-01

The underlying principles of the kinetics and equilibrium of a solitary sodium channel in the steady state are examined. Both the open and closed kinetics are postulated to result from round-trip excursions from a transition region that separates the openable and closed forms. Exponential behavior of the kinetics can have origins different from small-molecule systems. These differences suggest that the probability density functions (PDFs) that describe the time dependences of the open and closed forms arise from a distribution of rate constants. The distribution is likely to arise from a thermal modulation of the channel structure, and this provides a physical basis for the following three-variable equation: [formula; see text] Here, A0 is a scaling term, k is the mean rate constant, and sigma quantifies the Gaussian spread for the contributions of a range of effective rate constants. The maximum contribution is made by k, with rates faster and slower contributing less. (When sigma, the standard deviation of the spread, goes to zero, then p(f) = A0 e-kt.) The equation is applied to the single-channel steady-state probability density functions for batrachotoxin-treated sodium channels (1986. Keller et al. J. Gen. Physiol. 88: 1-23). The following characteristics are found: (a) The data for both open and closed forms of the channel are fit well with the above equation, which represents a Gaussian distribution of first-order rate processes. (b) The simple relationship [formula; see text] holds for the mean effective rat constants. Or, equivalently stated, the values of P open calculated from the k values closely agree with the P open values found directly from the PDF data. (c) In agreement with the known behavior of voltage-dependent rate constants, the voltage dependences of the mean effective rate constants for the opening and closing of the channel are equal and opposite over the voltage range studied. That is, [formula; see text] "Bursts" are related to the well-known cage effect of solution chemistry. PMID:1312365

Continuum theory of lipid bilayer electrostatics.

PubMed

Gerami, R; Bruinsma, R F

2009-10-01

In order to address the concerns about the applicability of the continuum theory of lipid bilayers, we generalize it by including a film with uniaxial dielectric properties representing the polar head groups of the lipid molecules. As a function of the in-plane dielectric constant κ|| of this film, we encounter a sequence of different phases. For low values of κ||, transmembrane pores have aqueous cores, ions are repelled by the bilayer, and the ion permeability of the bilayer is independent of the ion radius as in the existing theory. For increasing κ||, a threshold is reached--of the order of the dielectric constant of water--beyond which ions are attracted to the lipid bilayer by generic polarization attraction, transmembrane pores collapse, and the ion permeability becomes sensitively dependent on the ion radius, results that are more consistent with experimental and numerical studies of the interaction of ions with neutral lipid bilayers. At even higher values of κ||, the ion/pore complexes are predicted to condense in the form of extended arrays. The generalized continuum theory can be tested quantitatively by studies of the ion permeability as a function of salt concentration and co-surfactant concentration.

Nonlinear dielectric spectroscopy of propylene carbonate derivatives

NASA Astrophysics Data System (ADS)

Casalini, R.; Roland, C. M.

2018-04-01

Nonlinear dielectric measurements were carried out on two strongly polar liquids, 4-vinyl-1,3-dioxolan-2-one (VPC) and 4-ethyl-1,3-dioxolan-2-one (EPC), having chemical structures differing from propylene carbonate (PC) only by the presence of a pendant group. Despite their polarity, the compounds are all non-associated, "simple" liquids. From the linear component of the dielectric response, the α relaxation peak breadth was found to be invariant at a fixed value of the relaxation time, τα. From spectra from the nonlinear component, the number of dynamically correlated molecules was determined; it was also constant at fixed τα. Thus, two manifestations of dynamic heterogeneity depend only on the time constant for structural reorientation. More broadly, the cooperativity of molecular motions for non-associated glass-forming materials is connected to (i.e., reciprocally governs) the time scale. The equation of state for the two liquids was also obtained from density measurements made over a broad range of pressures and temperatures. Using these data, it was determined that the relaxation times of both liquids conform to density scaling. The effect of density, relative to thermal effects, on the α relaxation increases going from PC < VPC < EPC.

Electron-ion dissociative recombination rate constants relevant to the Titan atmosphere and the Interstellar Medium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Osborne, David; Lawson, Patrick; Adams, Nigel, E-mail: ngadams@uga.edu

Following the arrival of Cassini at Titan in 2004, the Titan atmosphere has been shown to contain large complex polycyclic-aromatic hydrocarbons. Since Cassini has provided a great deal of data, there exists a need for kinetic rate data to help with modeling this atmosphere. One type of kinetic data needed is electron-ion dissociative recombination (e-IDR) rate constants. These data are not readily available for larger compounds, such as naphthalene, or oxygen containing compounds, such as 1,4 dioxane or furan. Here, the rate constants for naphthalene, 1,4 dioxane, and furan have been measured and their temperature dependencies are determined when possible,more » using the University of Georgia's Variable Temperature Flowing Afterglow. The rate constants are compared with those previously published for other compounds; these show trends which illustrate the effects which multi-rings and oxygen heteroatoms substitutions have upon e-IDR rate constants.« less

Elastic constants of hcp 4He: Path-integral Monte Carlo results versus experiment

NASA Astrophysics Data System (ADS)

Ardila, Luis Aldemar Peña; Vitiello, Silvio A.; de Koning, Maurice

2011-09-01

The elastic constants of hcp 4He are computed using the path-integral Monte Carlo (PIMC) method. The stiffness coefficients are obtained by imposing different distortions to a periodic cell containing 180 atoms, followed by measurement of the elements of the corresponding stress tensor. For this purpose an appropriate path-integral expression for the stress tensor observable is derived and implemented into the pimc++ package. In addition to allowing the determination of the elastic stiffness constants, this development also opens the way to an explicit atomistic determination of the Peierls stress for dislocation motion using the PIMC technique. A comparison of the results to available experimental data shows an overall good agreement of the density dependence of the elastic constants, with the single exception of C13. Additional calculations for the bcc phase, on the other hand, show good agreement for all elastic constants.

Fast high-throughput method for the determination of acidity constants by capillary electrophoresis: I. Monoprotic weak acids and bases.

PubMed

Fuguet, Elisabet; Ràfols, Clara; Bosch, Elisabeth; Rosés, Martí

2009-04-24

A new and fast method to determine acidity constants of monoprotic weak acids and bases by capillary zone electrophoresis based on the use of an internal standard (compound of similar nature and acidity constant as the analyte) has been developed. This method requires only two electrophoretic runs for the determination of an acidity constant: a first one at a pH where both analyte and internal standard are totally ionized, and a second one at another pH where both are partially ionized. Furthermore, the method is not pH dependent, so an accurate measure of the pH of the buffer solutions is not needed. The acidity constants of several phenols and amines have been measured using internal standards of known pK(a), obtaining a mean deviation of 0.05 pH units compared to the literature values.

Electron-ion dissociative recombination rate constants relevant to the Titan atmosphere and the Interstellar Medium

NASA Astrophysics Data System (ADS)

Osborne, David; Lawson, Patrick; Adams, Nigel

2014-01-01

Following the arrival of Cassini at Titan in 2004, the Titan atmosphere has been shown to contain large complex polycyclic-aromatic hydrocarbons. Since Cassini has provided a great deal of data, there exists a need for kinetic rate data to help with modeling this atmosphere. One type of kinetic data needed is electron-ion dissociative recombination (e-IDR) rate constants. These data are not readily available for larger compounds, such as naphthalene, or oxygen containing compounds, such as 1,4 dioxane or furan. Here, the rate constants for naphthalene, 1,4 dioxane, and furan have been measured and their temperature dependencies are determined when possible, using the University of Georgia's Variable Temperature Flowing Afterglow. The rate constants are compared with those previously published for other compounds; these show trends which illustrate the effects which multi-rings and oxygen heteroatoms substitutions have upon e-IDR rate constants.

A universal reduced glass transition temperature for liquids

NASA Technical Reports Server (NTRS)

Fedors, R. F.

1979-01-01

Data on the dependence of the glass transition temperature on the molecular structure for low-molecular-weight liquids are analyzed in order to determine whether Boyer's reduced glass transition temperature (1952) is a universal constant as proposed. It is shown that the Boyer ratio varies widely depending on the chemical nature of the molecule. It is pointed out that a characteristic temperature ratio, defined by the ratio of the sum of the melting temperature and the boiling temperature to the sum of the glass transition temperature and the boiling temperature, is a universal constant independent of the molecular structure of the liquid. The average value of the ratio obtained from data for 65 liquids is 1.15.

CN radical reactions with hydrogen cyanide and cyanogen - Comparison of theory and experiment

NASA Technical Reports Server (NTRS)

Yang, D. L.; Yu, T.; Lin, M. C.; Melius, C. F.

1992-01-01

The method of laser photolysis/laser-induced fluorescence is used to obtain absolute rate constants for CN radical reactions with HCN and C2N2. The rate constants were found to be temperature-dependent in the range 300-740 K and pressure independent in the range 100-600 Torr. Rice-Remsperger-Kassel-Marcus theory for both reactions employing the transition state parameters obtained by the BAC-MP4 method are made. These calculations yielded reasonable results for the CN + HCN reaction, predicting both the temperature dependence and pressure independence. No pressure effect was observed in the pressure range 100-1000 Torr at temperatures below 900 K, confirming the experimental results.

Scaling laws for AC gas breakdown and implications for universality

NASA Astrophysics Data System (ADS)

Loveless, Amanda M.; Garner, Allen L.

2017-10-01

The reduced dependence on secondary electron emission and electrode surface properties makes radiofrequency (RF) and microwave (MW) plasmas advantageous over direct current (DC) plasmas for various applications, such as microthrusters. Theoretical models relating molecular constants to alternating current (AC) breakdown often fail due to incomplete understanding of both the constants and the mechanisms involved. This work derives simple analytic expressions for RF and MW breakdown, demonstrating the transition between these regimes at their high and low frequency limits, respectively. We further show that the limiting expressions for DC, RF, and MW breakdown voltage all have the same universal scaling dependence on pressure and gap distance at high pressure, agreeing with experiment.

Multiaxial Temperature- and Time-Dependent Failure Model

NASA Technical Reports Server (NTRS)

Richardson, David; McLennan, Michael; Anderson, Gregory; Macon, David; Batista-Rodriquez, Alicia

2003-01-01

A temperature- and time-dependent mathematical model predicts the conditions for failure of a material subjected to multiaxial stress. The model was initially applied to a filled epoxy below its glass-transition temperature, and is expected to be applicable to other materials, at least below their glass-transition temperatures. The model is justified simply by the fact that it closely approximates the experimentally observed failure behavior of this material: The multiaxiality of the model has been confirmed (see figure) and the model has been shown to be applicable at temperatures from -20 to 115 F (-29 to 46 C) and to predict tensile failures of constant-load and constant-load-rate specimens with failure times ranging from minutes to months..

Boson mapping techniques applied to constant gauge fields in QCD

NASA Technical Reports Server (NTRS)

Hess, Peter Otto; Lopez, J. C.

1995-01-01

Pairs of coordinates and derivatives of the constant gluon modes are mapped to new gluon-pair fields and their derivatives. Applying this mapping to the Hamiltonian of constant gluon fields results for large coupling constants into an effective Hamiltonian which separates into one describing a scalar field and another one for a field with spin two. The ground state is dominated by pairs of gluons coupled to color and spin zero with slight admixtures of color zero and spin two pairs. As color group we used SU(2).

A statistical evaluation of effective time constants of random telegraph noise with various operation timings of in-pixel source follower transistors

NASA Astrophysics Data System (ADS)

Yonezawa, A.; Kuroda, R.; Teramoto, A.; Obara, T.; Sugawa, S.

2014-03-01

We evaluated effective time constants of random telegraph noise (RTN) with various operation timings of in-pixel source follower transistors statistically, and discuss the dependency of RTN time constants on the duty ratio (on/off ratio) of MOSFET which is controlled by the gate to source voltage (VGS). Under a general readout operation of CMOS image sensor (CIS), the row selected pixel-source followers (SFs) turn on and not selected pixel-SFs operate at different bias conditions depending on the select switch position; when select switch locate in between the SF driver and column output line, SF drivers nearly turn off. The duty ratio and cyclic period of selected time of SF driver depends on the operation timing determined by the column read out sequence. By changing the duty ratio from 1 to 7.6 x 10-3, time constant ratio of RTN (time to capture <τc<)/(time to emission <τe<) of a part of MOSFETs increased while RTN amplitudes were almost the same regardless of the duty ratio. In these MOSFETs, <τc< increased and the majority of <τe< decreased and the minority of <τe< increased by decreasing the duty ratio. The same tendencies of behaviors of <τc< and <τe< were obtained when VGS was decreased. This indicates that the effective <τc< and <τe< converge to those under off state as duty ratio decreases. These results are important for the noise reduction, detection and analysis of in pixel-SF with RTN.

Responsiveness of the Care Dependency Scale for Rehabilitation (CDS-R).

PubMed

Eichhorn-Kissel, Juliane; Dassen, Theo; Lohrmann, Christa

2012-03-01

Around 10% of Western Europe's population suffer from a disability which can entail a decrease of independency and quality of life. However, the lives of these people can be improved by rehabilitative treatment and care. Changing the degree of dependency from dependent to independent is essential in rehabilitation, as is the assessment of these changes. To perform such kind of measurements, assessment instruments have to be responsive. In spite of this concern, responsiveness of assessment instruments is studied to a small extent only. This also applies to the Care Dependency Scale for Rehabilitation (CDS-R), a short assessment instrument measuring the care dependency of patients regarding physical and psychosocial aspects. In this longitudinal-study, the responsiveness of the CDS-R, in general and related to different disease-groups, should be determined. Therefore, a convenience sample of 1564 patients was assessed in an Austrian rehabilitation centre with the scale after admission and before discharge. Responsiveness was determined by descriptive analysis, calculation of effect-sizes and significance tests. Differences between admission and discharge occurred on a statistically significant level for patients who changed. Kazis' effect-sizes can be considered as of small/medium effect for patients who changed (0.24/0.49), and as of large effect according to Liang (0.86/1.46). Eta squared was 0.10/0.19 which can be interpreted as of moderate/large effect for patients who changed. Responsiveness-analyses related to different disease-groups showed constantly large effect-sizes for patients with musculoskeletal-disorders. These results indicate that the CDS-R can detect patient-changes over time and discriminate between patients who change under rehabilitation or not. These aspects argue for the responsiveness of the scale, wherefore the CDS-R seems to be appropriate for the assessment of treatment/health-care effectiveness and the evaluation of individual patient-changes. Nevertheless further research is recommended to confirm the level of responsiveness of the scale in general and for different disease-groups. © 2011 The Authors. Scandinavian Journal of Caring Sciences © 2011 Nordic College of Caring Science.

Pressure-derived indices of left ventricular isovolumic relaxation in patients with hypertrophic cardiomyopathy.

PubMed Central

Thompson, D S; Wilmshurst, P; Juul, S M; Waldron, C B; Jenkins, B S; Coltart, D J; Webb-Peploe, M M

1983-01-01

High fidelity measurements of left ventricular pressure were made at increasing pacing rates in 21 patients with hypertrophic cardiomyopathy and a control group of 11 patients investigated for chest pain who proved to have normal hearts. In both groups the fall in pressure during isovolumic relaxation from the point of min dp/dt approximated closely to a monoexponential, and could be described by a time constant and asymptote. The time constant shortened and the asymptote increased as heart rate rose in both groups. The time constant was longer and min dp/dt less in the cardiomyopathy group than controls at all heart rates. In the cardiomyopathy patients min dp/dt, but not the time constant, was related to systolic pressure. During pacing, eight cardiomyopathy patients developed metabolic evidence of myocardial ischaemia, but indices of relaxation did not differ between these eight and the other 13 either at basal heart rate or the highest pacing rate. In 10 cardiomyopathy patients measurements were repeated at comparable pacing rates after propranolol (0.2 mg/kg). Left ventricular end-diastolic pressure and indices of contractility decreased after the drug, but the time constant did not change. Eight patients received verapamil (20 mg) after which there were substantial reductions in systolic pressure and contractility. Min dp/dt decreased in proportion to systolic pressure, but the time constant was unchanged. At the highest pacing rate before drug administration three patients had abnormal lactate extraction which was corrected by either propranolol (one patient) or verapamil (two patients). Despite abolition of metabolic evidence of ischaemia, relaxation did not improve. It is concluded that abnormal isovolumic relaxation is common in patients with hypertrophic cardiomyopathy, but its severity correlates poorly with other features of the disease. Abnormal relaxation is not the result of ischaemia, and pressure derived indices of relaxation do not improve after the administration of propranolol or verapamil. PMID:6681978

E-health empowers patients with ulcerative colitis: a randomised controlled trial of the web-guided 'Constant-care' approach.

PubMed

Elkjaer, Margarita; Shuhaibar, Mary; Burisch, Johan; Bailey, Yvonne; Scherfig, Hanne; Laugesen, Birgit; Avnstrøm, Søren; Langholz, Ebbe; O'Morain, Colm; Lynge, Elsebeth; Munkholm, Pia

2010-12-01

The natural history of ulcerative colitis requires continuous monitoring of medical treatment via frequent outpatient visits. The European health authorities' focus on e-health is increasing. Lack of easy access to inflammatory bowel disease (IBD) clinics, patients' education and understanding of the importance of early treatment at relapse is leading to poor compliance. To overcome these limitations a randomised control trial 'Constant-care' was undertaken in Denmark and Ireland. 333 patients with mild/moderate ulcerative colitis and 5-aminosalicylate acid treatment were randomised to either a web-group receiving disease specific education and self-treatment via http://www.constant-care.dk or a control group continuing the usual care for 12 months. A historical control group was included to test the comparability with the control group. We investigated: feasibility of the approach, its influence on patients' compliance, knowledge, quality of life (QoL), disease outcomes, safety and health care costs. 88% of the web patients preferred using the new approach. Adherence to 4 weeks of acute treatment was increased by 31% in Denmark and 44% in Ireland compared to the control groups. In Denmark IBD knowledge and QoL were significantly improved in web patients. Median relapse duration was 18 days (95% CI 10 to 21) in the web versus 77 days (95% CI 46 to 108) in the control group. The number of acute and routine visits to the outpatient clinic was lower in the web than in the control group, resulting in a saving of 189 euro/patient/year. No difference in the relapse frequency, hospitalisation, surgery or adverse events was observed. The historical control group was comparable with the control group. The new web-guided approach on http://www.constant-care.dk is feasible, safe and cost effective. It empowers patients with ulcerative colitis without increasing their morbidity and depression. It has yet to be shown whether this strategy can change the natural disease course of ulcerative colitis in the long term.

Dependency distances in natural mixed languages. Comment on "Dependency distance: A new perspective on syntactic patterns in natural languages" by Haitao Liu et al.

NASA Astrophysics Data System (ADS)

Wang, Lin

2017-07-01

Haitao Liu et al.'s article [1] offers a comprehensive account of the diversity of syntactic patterns in human languages in terms of an important index of memory burden and syntactic difficulty - the dependency distance. Natural languages, a complex system, present overall shorter dependency distances under the universal pressure for dependency distance minimization; however, there exist some relatively-long-distance dependencies, which reflect that language can constantly adapt itself to some deep-level biological or functional constraints.

Self-Consistency of the Lauritzen-Hoffman and Strobl Models of Polymer Crystallization Evaluated for Poly(epsilon-caprolactone) Fractions and Effect of Composition on the Phenomenon of Concurrent Crystallization in Polyethylene Blends

NASA Astrophysics Data System (ADS)

Sheth, Swapnil Suhas

Narrow molecular weight fractions of poly(epsilon-caprolactone) were successfully obtained using the successive precipitation fractionation technique with toluene/n-heptane as a solvent/nonsolvent pair. Calorimetric studies of the melting behavior of fractions that were crystallized either isothermally or under constant cooling rate conditions suggested that the isothermal crystallization of the samples should be used for a proper evaluation of the molecular weight dependence of the observed melting temperature and degree of crystallinity in PCL. The molecular weight and temperature dependence of the spherulitic growth rate of fractions was studied in the context of the Lauritzen-Hoffman two-phase model and the Strobl three-phase model of polymer crystallization. The zero-growth rate temperatures, determined from spherulitic growth rates using four different methods, are consistent with each other and increase with chain length. The concomitant increase in the apparent secondary nucleation constant was attributed to two factors. First, for longer chains there is an increase in the probability that crystalline stems belong to loose chain-folds, hence, an increase in fold surface free energy. It is speculated that the increase in loose folding and resulting decrease in crystallinity with increasing chain length are associated with the ester group registration requirement in PCL crystals. The second contribution to the apparent nucleation constant arises from chain friction associated with segmental transport across the melt/crystal interface. These factors were responsible for the much stronger chain length dependence of spherulitic growth rates at fixed undercooling observed here with PCL than previously reported for PE and PEO. In the case of PCL, the scaling exponent associated with the chain length dependence of spherulitic growth rates exceeds the upper theoretical bound of 2 predicted from the Brochard- DeGennes chain pullout model. Observation that zero-growth and equilibrium melting temperature values are identical with each other within the uncertainty of their determinations casts serious doubt on the validity of Strobl three-phase model. A novel method is proposed to determine the Porod constant necessary to extrapolate the small angle X-ray scattering intensity data to large scattering vectors. The one-dimensional correlation function determined using this Porod constant yielded the values of lamellar crystal thickness, which were similar to these estimated using the Hosemann-Bagchi Paracrystalline Lattice model. The temperature dependence of the lamellar crystal thickness was consistent with both LH and the Strobl model of polymer crystallization. However, in contrast to the predictions of Strobl's model, the value of the mesomorph-to-crystal equilibrium transition temperature was very close to the zero-growth temperature. Moreover, the lateral block sizes (obtained using wide angle X-ray diffraction) and the lamellar thicknesses were not found to be controlled by the mesomorph-to-crystal equilibrium transition temperature. Hence, we concluded that the crystallization of PCL is not mediated by a mesophase. Metallocene-catalyzed linear low-density (m-LLDPE with 3.4 mol% 1-octene) and conventional low-density (LDPE) polyethylene blends of different compositions were investigated for their melt-state miscibility and concurrent crystallization tendency. Differential scanning calorimetric studies and morphological studies using atomic force microscopy confirm that these blends are miscible in the melt-state for all compositions. LDPE chains are found to crystallize concurrently with m-LLDPE chains during cooling in the m-LLDPE crystallization temperature range. While the extent of concurrent crystallization was found to be optimal in .. .. iv blends with highest m-LLDPE content studied, strong evidence was uncovered for the existence of a saturation effect in the concurrent crystallization behavior. This observation leads us to suggest that co-crystallization, rather than mere concurrent crystallization, of LDPE with m- LLDPE can indeed take place. Matching of the respective sequence length distributions in LDPE and m-LLDPE is suggested to control the extent of co-crystallization.

Effects of ionic concentration gradient on electroosmotic flow mixing in a microchannel.

PubMed

Peng, Ran; Li, Dongqing

2015-02-15

Effects of ionic concentration gradient on electroosmotic flow (EOF) mixing of one stream of a high concentration electrolyte solution with a stream of a low concentration electrolyte solution in a microchannel are investigated numerically. The concentration field, flow field and electric field are strongly coupled via concentration dependent zeta potential, dielectric constant and electric conductivity. The results show that the electric field and the flow velocity are non-uniform when the concentration dependence of these parameters is taken into consideration. It is also found that when the ionic concentration of the electrolyte solution is higher than 1M, the electrolyte solution essentially cannot enter the channel due to the extremely low electroosmotic flow mobility. The effects of the concentration dependence of zeta potential, dielectric constant and electric conductivity on electroosmotic flow mixing are studied. Copyright © 2014 Elsevier Inc. All rights reserved.

Variable horizon in a peridynamic medium

DOE PAGES

Silling, Stewart A.; Littlewood, David J.; Seleson, Pablo

2015-12-10

Here, a notion of material homogeneity is proposed for peridynamic bodies with variable horizon but constant bulk properties. A relation is derived that scales the force state according to the position-dependent horizon while keeping the bulk properties unchanged. Using this scaling relation, if the horizon depends on position, artifacts called ghost forces may arise in a body under a homogeneous deformation. These artifacts depend on the second derivative of the horizon and can be reduced by employing a modified equilibrium equation using a new quantity called the partial stress. Bodies with piecewise constant horizon can be modeled without ghost forcesmore » by using a simpler technique called a splice. As a limiting case of zero horizon, both the partial stress and splice techniques can be used to achieve local-nonlocal coupling. Computational examples, including dynamic fracture in a one-dimensional model with local-nonlocal coupling, illustrate the methods.« less

High coronal structure of high velocity solar wind stream sources

NASA Technical Reports Server (NTRS)

Nolte, J. T.; Krieger, A. S.; Roelof, E. C.; Gold, R. E.

1977-01-01

It is shown analytically that the transition from a high-speed stream source to the ambient coronal conditions is quite rapid in longitude in the high corona. This sharp eastern coronal boundary for the solar wind stream sources is strongly suggested by the solar wind 'dwells' which appear in plots of solar wind velocity against constant-radial-velocity-approximation source longitudes. The possibility of a systematic velocity-dependent effect in the constant-radial-velocity approximation, which would cause this boundary to appear sharper than it is, is investigated. A velocity-dependent interplanetary propagation effect or a velocity-dependent 'source altitude' are two possible sources of such a systematic effect. It is shown that, for at least some dwells, significant interplanetary effects are not likely. The variation of the Alfvenic critical radius in solar wind dwells is calculated, showing that the high-velocity stream originates from a significantly lower altitude than the ambient solar wind.

Transient Dynamics of Double Quantum Dots Coupled to Two Reservoirs

NASA Astrophysics Data System (ADS)

Fukadai, Takahisa; Sasamoto, Tomohiro

2018-05-01

We study the time-dependent properties of double quantum dots coupled to two reservoirs using the nonequilibrium Green function method. For an arbitrary time-dependent bias, we derive an expression for the time-dependent electron density of a dot and several currents, including the current between the dots in the wide-band-limit approximation. For the special case of a constant bias, we calculate the electron density and the currents numerically. As a result, we find that these quantities oscillate and that the number of crests in a single period of the current from a dot changes with the bias voltage. We also obtain an analytical expression for the relaxation time, which expresses how fast the system converges to its steady state. From the expression, we find that the relaxation time becomes constant when the coupling strength between the dots is sufficiently large in comparison with the difference of coupling strength between the dots and the reservoirs.

Huge domain-wall speed variation with respect to ferromagnetic layer thickness in ferromagnetic Pt/Co/TiO2/Pt films

NASA Astrophysics Data System (ADS)

Kim, Dae-Yun; Park, Min-Ho; Park, Yong-Keun; Yu, Ji-Sung; Kim, Joo-Sung; Kim, Duck-Ho; Min, Byoung-Chul; Choe, Sug-Bong

2018-02-01

In this study, we investigate the influence of the ferromagnetic layer thickness on the magnetization process. A series of ultrathin Pt/Co/TiO2/Pt films exhibits domain-wall (DW) speed variation of over 100,000 times even under the same magnetic field, depending on the ferromagnetic layer thickness. From the creep-scaling analysis, such significant variation is found to be mainly attributable to the thickness-dependence of the creep-scaling constant in accordance with the creep-scaling theory of the linear proportionality between the creep-scaling constant and the ferromagnetic layer thickness. Therefore, a thinner film shows a faster DW speed. The DW roughness also exhibits sensitive dependence on the ferromagnetic layer thickness: a thinner film shows smoother DW. The present observation provided a guide for an optimal design rule of the ferromagnetic layer thickness for better performance of DW-based devices.

Genistein Binding to Copper(II)-Solvent Dependence and Effects on Radical Scavenging.

PubMed

Yang, Jing; Xu, Yi; Liu, Hao-Yu; Han, Rui-Min; Zhang, Jian-Ping; Skibsted, Leif H

2017-10-18

Genistein, but not daidzein, binds to copper(II) with a 1:2 stoichiometry in ethanol and with a 1:1 stoichiometry in methanol, indicating chelation by the 5-phenol and the 4-keto group of the isoflavonoid as demonstrated by the Jobs method and UV-visible absorption spectroscopy. In ethanol, the stability constants had the value 1.12 × 10 11 L²∙mol -2 for the 1:2 complex and in methanol 6.0 × 10⁵ L∙mol -1 for the 1:1 complex at 25 °C. Binding was not detected in water, as confirmed by an upper limit for the 1:1 stability constant of K = 5 mol -1 L as calculated from the difference in solvation free energy of copper(II) between methanol and the more polar water. Solvent molecules compete with genistein as demonstrated in methanol where binding stoichiometry changes from 1:2 to 1:1 compared to ethanol and methanol/chloroform (7/3, v / v ). Genistein binding to copper(II) increases the scavenging rate of the stable, neutral 2,2-diphenyl-1-picrylhydrazyl radical by more than a factor of four, while only small effects were seen for the short-lived but more oxidizing β -carotene radical cation using laser flash photolysis. The increased efficiency of coordinated genistein is concluded to depend on kinetic rather than on thermodynamic factors, as confirmed by the small change in reduction potential of -0.016 V detected by cyclic voltammetry upon binding of genistein to copper(II) in methanol/chloroform solutions.

Viscosity Relaxation in Molten HgZnTe

NASA Technical Reports Server (NTRS)

Su, Ching-Hua; Lehoczky, S. L.; Kim, Yeong Woo; Baird, James K.; Whitaker, Ann F. (Technical Monitor)

2001-01-01

Rotating cup measurements of the viscosity of the pseudo-binary melt, HgZnTe have shown that the isothermal liquid with zinc mole fraction 0.16 requires tens of hours of equilibration time before a steady viscous state can be achieved. Over this relaxation period, the viscosity at 790 C increases by a factor of two, while the viscosity at 810 C increases by 40%. Noting that the Group VI elements tend to polymerize when molten, we suggest that the viscosity of the melt is enhanced by the slow formation of Te atom chains. To explain the build-up of linear Te n-mers, we propose a scheme, which contains formation reactions with second order kinetics that increase the molecular weight, and decomposition reactions with first order kinetics that inactivate the chains. The resulting rate equations can be solved for the time dependence of each molecular weight fraction. Using these molecular weight fractions, we calculate the time dependence of the average molecular weight. Using the standard semi-empirical relation between polymer average molecular weight and viscosity, we then calculate the viscosity relaxation curve. By curve fitting, we find that the data imply that the rate constant for n-mer formation is much smaller than the rate constant for n-mer deactivation, suggesting that Te atoms only weakly polymerize in molten HgZnTe. The steady state toward which the melt relaxes occurs as the rate of formation of an n-mer becomes exactly balanced by the sum of the rate for its deactivation and the rate for its polymerization to form an (n+1)-mer.

Comparing otoacoustic emissions evoked by chirp transients with constant absorbed sound power and constant incident pressure magnitude.

PubMed

Keefe, Douglas H; Feeney, M Patrick; Hunter, Lisa L; Fitzpatrick, Denis F

2017-01-01

Human ear-canal properties of transient acoustic stimuli are contrasted that utilize measured ear-canal pressures in conjunction with measured acoustic pressure reflectance and admittance. These data are referenced to the tip of a probe snugly inserted into the ear canal. Promising procedures to calibrate across frequency include stimuli with controlled levels of incident pressure magnitude, absorbed sound power, and forward pressure magnitude. An equivalent pressure at the eardrum is calculated from these measured data using a transmission-line model of ear-canal acoustics parameterized by acoustically estimated ear-canal area at the probe tip and length between the probe tip and eardrum. Chirp stimuli with constant incident pressure magnitude and constant absorbed sound power across frequency were generated to elicit transient-evoked otoacoustic emissions (TEOAEs), which were measured in normal-hearing adult ears from 0.7 to 8 kHz. TEOAE stimuli had similar peak-to-peak equivalent sound pressure levels across calibration conditions. Frequency-domain TEOAEs were compared using signal level, signal-to-noise ratio (SNR), coherence synchrony modulus (CSM), group delay, and group spread. Time-domain TEOAEs were compared using SNR, CSM, instantaneous frequency and instantaneous bandwidth. Stimuli with constant incident pressure magnitude or constant absorbed sound power across frequency produce generally similar TEOAEs up to 8 kHz.

Dependence of Interfacial Dzyaloshinskii-Moriya Interaction on Layer Thicknesses in Ta /Co -Fe -B /TaOx Heterostructures from Brillouin Light Scattering

NASA Astrophysics Data System (ADS)

Chaurasiya, Avinash Kumar; Choudhury, Samiran; Sinha, Jaivardhan; Barman, Anjan

2018-01-01

The interfacial Dzyaloshinskii-Moriya interaction (IDMI) has recently drawn extensive research interest due to its fundamental role in stabilizing chiral spin textures in ultrathin ferromagnets, which are suitable candidates for future magnetic-memory devices. Here, we explore the ferromagnetic and heavy-metal layer-thickness dependence of IDMI in technologically important Ta /Co20Fe60B20/TaOx heterostructures by measuring nonreciprocity in spin-wave frequency using the Brillouin light-scattering technique. The observed value of the IDMI constant agrees with that obtained from a separate measurement of in-plane angular dependence of frequency nonreciprocity, which is also in good agreement with the theory predicted by Cortes-Ortuno and Landeros. Linear scaling behavior of IDMI with the inverse of Co-Fe-B thicknesses suggests that IDMI originates primarily from the interface in these heterostructures, whereas we observe a weak dependence of Ta thickness on the strength of IDMI. Importantly, the observed value of the IDMI constant is reasonably large by a factor of 3 compared to annealed Ta /Co -Fe -B /MgO heterostructures. We propose that the observation of large IDMI is likely due to the absence of boron diffusion towards the Ta /Co -Fe -B interface as the heterostructures are as deposited. Our detailed investigation opens up a route to designing thin-film heterostructures with the tailored IDMI constant for controlling Skyrmion-based magnetic-memory devices.

Cavitation Damage Experiments for Mercury Spallation Targets At the LANSCE WNR in 2008

DOE Office of Scientific and Technical Information (OSTI.GOV)

Riemer, Bernie; Wendel, Mark W; Felde, David K

2010-01-01

Proton beam experiments investigating cavitation damage in short pulse mercury spallation targets were performed at LANSCE WNR in July of 2008. They included two main areas for investigation: damage dependence on mercury velocity using geometry more prototypic to the SNS target than previously employed and damage dependence on incident proton beam flux intensity. The flow dependence experiment employed six test targets with mercury velocity in the channel ranging from 0 to more than 4 m/s. Each was hit with 100 WNR beam pulses with peak proton flux equivalent to that of SNS operating at 2.7 MW. Damage dependence on incidentmore » proton beam flux intensity was also investigated with three intensity levels used on simple rectangular shaped targets without mercury flow. Intensity variation was imposed by focusing the beam differently while maintaining protons per pulse. This kept total energy deposited in each target constant. A fourth test target was hit with various beams: constant protons and varied spot size; constant spot size and varied protons. No damage will be assessed in this case. Instead, acoustic emissions associated with cavitation collapse were measured by laser Doppler vibrometer (LDV) from readings of exterior vessel motions as well as by mercury wetted acoustic transducers. This paper will provide a description of the experiment and present available results. Damage assessment will require several months before surface analysis can be completed and was not available in time for IWSMT-9.« less

Synaptic convergence regulates synchronization-dependent spike transfer in feedforward neural networks.

PubMed

Sailamul, Pachaya; Jang, Jaeson; Paik, Se-Bum

2017-12-01

Correlated neural activities such as synchronizations can significantly alter the characteristics of spike transfer between neural layers. However, it is not clear how this synchronization-dependent spike transfer can be affected by the structure of convergent feedforward wiring. To address this question, we implemented computer simulations of model neural networks: a source and a target layer connected with different types of convergent wiring rules. In the Gaussian-Gaussian (GG) model, both the connection probability and the strength are given as Gaussian distribution as a function of spatial distance. In the Uniform-Constant (UC) and Uniform-Exponential (UE) models, the connection probability density is a uniform constant within a certain range, but the connection strength is set as a constant value or an exponentially decaying function, respectively. Then we examined how the spike transfer function is modulated under these conditions, while static or synchronized input patterns were introduced to simulate different levels of feedforward spike synchronization. We observed that the synchronization-dependent modulation of the transfer function appeared noticeably different for each convergence condition. The modulation of the spike transfer function was largest in the UC model, and smallest in the UE model. Our analysis showed that this difference was induced by the different spike weight distributions that was generated from convergent synapses in each model. Our results suggest that, the structure of the feedforward convergence is a crucial factor for correlation-dependent spike control, thus must be considered important to understand the mechanism of information transfer in the brain.

Computation of restoration of ligand response in the random kinetics of a prostate cancer cell signaling pathway.

PubMed

Dana, Saswati; Nakakuki, Takashi; Hatakeyama, Mariko; Kimura, Shuhei; Raha, Soumyendu

2011-01-01

Mutation and/or dysfunction of signaling proteins in the mitogen activated protein kinase (MAPK) signal transduction pathway are frequently observed in various kinds of human cancer. Consistent with this fact, in the present study, we experimentally observe that the epidermal growth factor (EGF) induced activation profile of MAP kinase signaling is not straightforward dose-dependent in the PC3 prostate cancer cells. To find out what parameters and reactions in the pathway are involved in this departure from the normal dose-dependency, a model-based pathway analysis is performed. The pathway is mathematically modeled with 28 rate equations yielding those many ordinary differential equations (ODE) with kinetic rate constants that have been reported to take random values in the existing literature. This has led to us treating the ODE model of the pathways kinetics as a random differential equations (RDE) system in which the parameters are random variables. We show that our RDE model captures the uncertainty in the kinetic rate constants as seen in the behavior of the experimental data and more importantly, upon simulation, exhibits the abnormal EGF dose-dependency of the activation profile of MAP kinase signaling in PC3 prostate cancer cells. The most likely set of values of the kinetic rate constants obtained from fitting the RDE model into the experimental data is then used in a direct transcription based dynamic optimization method for computing the changes needed in these kinetic rate constant values for the restoration of the normal EGF dose response. The last computation identifies the parameters, i.e., the kinetic rate constants in the RDE model, that are the most sensitive to the change in the EGF dose response behavior in the PC3 prostate cancer cells. The reactions in which these most sensitive parameters participate emerge as candidate drug targets on the signaling pathway. 2011 Elsevier Ireland Ltd. All rights reserved.

Structure-activity correlations for organophosphorus ester anticholinesterases. Part 2: CNDO/2 calculations applied to ester hydrolysis rates

NASA Technical Reports Server (NTRS)

Johnson, H.; Kenley, R. A.; Rynard, C.; Golub, M. A.

1984-01-01

Quantitative structure-activity relationships are presented for the hydrolysis of organophosphorus esters, RR'P(O)X, where R and R' are alkyl and/or alkoxy groups and X is fluorine, chlorine or a phenoxy group. CNDO/2 calculations provide values for molecular parameters that correlate with alkaline hydrolysis rates. For each subset of esters with the same leaving group, X, the CNDO-derived net atomic charge at the central phosphorus atom correlates well with the alkaline hydrolysis rate constants. For the whole set of esters with different leaving groups, equations are derived that relate charge, orbital energy and bond order to the hydrolysis rate constants.

[Superbrown beauty : The surface of tanorexia and tanning dependence].

PubMed

Harth, W

2017-12-01

Brown skin symbolizes fitness, health, youthfulness and beauty, combined with leisure, activity, and joy of life in the Central European culture. Tanorexia is a tanning dependence that describes the morbid excessive desire for constant skin tanning. Particularly young women are affected. This article shows the underlying psychodermatological disorders.

Control of the Protein Turnover Rates in Lemna minor

PubMed Central

Trewavas, A.

1972-01-01

The control of protein turnover in Lemna minor has been examined using a method described in the previous paper for determining the rate constants of synthesis and degradation of protein. If Lemna is placed on water, there is a reduction in the rate constants of synthesis of protein and an increase (3- to 6-fold) in the rate constant of degradation. The net effect is a loss of protein from the tissue. Omission of nitrate, phosphate, sulfate, magnesium, or calcium results in increases in the rate constant of degradation of protein. An unusual dual effect of benzyladenine on the turnover constants has been observed. Treatment of Lemna grown on sucrose-mineral salts with benzyladenine results in alterations only in the rate constant of synthesis. Treatment of Lemna grown on water with benzyladenine alters only the rate constant of degradation. Abscisic acid on the other hand alters both rate constants of synthesis and degradation of protein together. Inclusion of growth-inhibiting amino acids in the medium results in a reduction in the rate constants of synthesis and increases in the rate constant of degradation of protein. It is concluded that the rate of turnover of protein in Lemna is very dependent on the composition of the growth medium. Conditions which reduce growth rates also reduce the rates of synthesis of protein and increase those of degradation. PMID:16657895

The effect of solvent relaxation time constants on free energy gap law for ultrafast charge recombination following photoinduced charge separation.

PubMed

Mikhailova, Valentina A; Malykhin, Roman E; Ivanov, Anatoly I

2018-05-16

To elucidate the regularities inherent in the kinetics of ultrafast charge recombination following photoinduced charge separation in donor-acceptor dyads in solutions, the simulations of the kinetics have been performed within the stochastic multichannel point-transition model. Increasing the solvent relaxation time scales has been shown to strongly vary the dependence of the charge recombination rate constant on the free energy gap. In slow relaxing solvents the non-equilibrium charge recombination occurring in parallel with solvent relaxation is very effective so that the charge recombination terminates at the non-equilibrium stage. This results in a crucial difference between the free energy gap laws for the ultrafast charge recombination and the thermal charge transfer. For the thermal reactions the well-known Marcus bell-shaped dependence of the rate constant on the free energy gap is realized while for the ultrafast charge recombination only a descending branch is predicted in the whole area of the free energy gap exceeding 0.2 eV. From the available experimental data on the population kinetics of the second and first excited states for a series of Zn-porphyrin-imide dyads in toluene and tetrahydrofuran solutions, an effective rate constant of the charge recombination into the first excited state has been calculated. The obtained rate constant being very high is nearly invariable in the area of the charge recombination free energy gap from 0.2 to 0.6 eV that supports the theoretical prediction.

Constant-concentration boundary condition: Lessons from the HYDROCOIN variable-density groundwater benchmark problem

USGS Publications Warehouse

Konikow, Leonard F.; Sanford, W.E.; Campbell, P.J.

1997-01-01

In a solute-transport model, if a constant-concentration boundary condition is applied at a node in an active flow field, a solute flux can occur by both advective and dispersive processes. The potential for advective release is demonstrated by reexamining the Hydrologic Code Intercomparison (HYDROCOIN) project case 5 problem, which represents a salt dome overlain by a shallow groundwater system. The resulting flow field includes significant salinity and fluid density variations. Several independent teams simulated this problem using finite difference or finite element numerical models. We applied a method-of-characteristics model (MOCDENSE). The previous numerical implementations by HYDROCOIN teams of a constant-concentration boundary to represent salt release by lateral dispersion only (as stipulated in the original problem definition) was flawed because this boundary condition allows the release of salt into the flow field by both dispersion and advection. When the constant-concentration boundary is modified to allow salt release by dispersion only, significantly less salt is released into the flow field. The calculated brine distribution for case 5 depends very little on which numerical model is used, as long as the selected model is solving the proper equations. Instead, the accuracy of the solution depends strongly on the proper conceptualization of the problem, including the detailed design of the constant-concentration boundary condition. The importance and sensitivity to the manner of specification of this boundary does not appear to have been recognized previously in the analysis of this problem.

Bimolecular Rate Constants for FAD-Dependent Glucose Dehydrogenase from Aspergillus terreus and Organic Electron Acceptors.

PubMed

Tsuruoka, Nozomu; Sadakane, Takuya; Hayashi, Rika; Tsujimura, Seiya

2017-03-10

The flavin adenine dinucleotide-dependent glucose dehydrogenase (FAD-GDH) from Aspergillus species require suitable redox mediators to transfer electrons from the enzyme to the electrode surface for the application of bioelectrical devices. Although several mediators for FAD-GDH are already in use, they are still far from optimum in view of potential, kinetics, sustainability, and cost-effectiveness. Herein, we investigated the efficiency of various phenothiazines and quinones in the electrochemical oxidation of FAD-GDH from Aspergillus terreus . At pH 7.0, the logarithm of the bimolecular oxidation rate constants appeared to depend on the redox potentials of all the mediators tested. Notably, the rate constant of each molecule for FAD-GDH was approximately 2.5 orders of magnitude higher than that for glucose oxidase from Aspergillus sp. The results suggest that the electron transfer kinetics is mainly determined by the formal potential of the mediator, the driving force of electron transfer, and the electron transfer distance between the redox active site of the mediator and the FAD, affected by the steric or chemical interactions. Higher k ₂ values were found for ortho-quinones than for para-quinones in the reactions with FAD-GDH and glucose oxidase, which was likely due to less steric hindrance in the active site in the case of the ortho-quinones.

Multiferroic properties of Indian natural ilmenite

NASA Astrophysics Data System (ADS)

Acharya, Truptimayee; Choudhary, R. N. P.

2017-03-01

In this communication, the main results and analysis of extensive studies of electric and magnetic characteristics (relative dielectric constant, tangent loss, electric polarization, electric transport, impedance, magnetic polarization and magneto-electric coupling coefficient) of Indian natural ilmenite (NI) have been presented. Preliminary structural analysis was studied by Rietveld refinement of room temperature XRD data, which suggests the rhombohedral crystal system of NI. Maxwell-Wagner mechanism was used to explain the nature of the frequency dependence of the relative dielectric constant. The impedance analysis reveals that below 270 °C, only the bulk contributes, whereas at higher temperature, both grain boundary and the bulk contribute to the resistive characteristics of the material. The magnitude of the depression angles of the semicircles in the Nyquist plot has been estimated. The correlated barrier hopping model has been used to explain the frequency dependence of ac conductivity of the material. The activation energy of the compound has been estimated using the temperature dependence of dc conductivity plot. The obtained polarization hysteresis loops manifest improper ferroelectric behavior of NI. The existence M-H hysteresis loop supports anti-ferromagnetism in the studied material. The magneto-electric voltage coupling coefficient is found to be 0.7 mV/cm Oe. Hence, other than dielectric constant, electric polarization, magnetization and magneto-electric studies support the existence of multiferroic properties in NI.

Voltage dependence of acetylcholine receptor channel gating in rat myoballs

PubMed Central

1992-01-01

Whole-cell currents from nicotinic acetylcholine receptor (AChR) channels were studied in rat myoballs using a light-activated agonist to determine the voltage dependence of the macroscopic opening and closing rate constants. Myoballs were bathed in a solution containing a low concentration of the inactive isomer of the photoisomerizable azobenzene derivative, cis-Bis-Q. A light flash was then presented to produce a known concentration jump of agonist, trans-Bis-Q, across a wide range of membrane potentials in symmetrical solutions (NaCl or CsCl on both sides) or asymmetrical solutions (NaCl in the bath and CsCl in the pipette). At the low agonist concentration used in this study, the reciprocal of the macroscopic time constants gives an unambiguous measure of the effective closing rate. It showed an exponential decrease with membrane hyperpolarization between +20 and - 100 mV, but tended to level off at more depolarized and at more hyperpolarized membrane potentials. The relative effective opening rate was derived from the steady-state conductance, the single-channel conductance, and the apparent closing rate; it decreased sharply in the depolarizing region and tended to level off and then turn up in the hyperpolarizing region. The two effective rate constants were shown to depend on the first, second, and third power of membrane potential. PMID:1460456

Some new results on the Levy, Levy and Solomon microscopic stock market model

NASA Astrophysics Data System (ADS)

Zschischang, Elmar; Lux, Thomas

2001-03-01

We report some findings from our simulations of the Levy, Levy and Solomon microscopic stock market model. Our results cast doubts on some of the results published in the original papers (i.e., chaotic stock price movements). We also point out the possibility of sensitive dependence on initial conditions of the emerging wealth distribution among agents. Extensions of the model set-up show that with varying degrees of risk aversion, the less risk averse traders will tend to dominate the market. Similarly, when introducing a new trader group (or even a single trader) with a constant share of stocks in their portfolio, the latter will eventually take over and marginalize the other groups. The better performance of the more sober investors is in accordance with traditional perceptions in financial economics. Hence, the survival of ‘noise traders’ looking at short-term trends and patterns remains as much of a puzzle in this framework as in the traditional Efficient Market Theory.

Nonequilibrium Kondo effect in a magnetic field: auxiliary master equation approach

NASA Astrophysics Data System (ADS)

Fugger, Delia M.; Dorda, Antonius; Schwarz, Frauke; von Delft, Jan; Arrigoni, Enrico

2018-01-01

We study the single-impurity Anderson model out of equilibrium under the influence of a bias voltage ϕ and a magnetic field B. We investigate the interplay between the shift ({ω }B) of the Kondo peak in the spin-resolved density of states (DOS) and the one ({φ }B) of the conductance anomaly. In agreement with experiments and previous theoretical calculations we find that, while the latter displays a rather linear behavior with an almost constant slope as a function of B down to the Kondo scale, the DOS shift first features a slower increase reaching the same behavior as {φ }B only for | g| {μ }BB\\gg {k}B{T}K. Our auxiliary master equation approach yields highly accurate nonequilibrium results for the DOS and for the conductance all the way from within the Kondo up to the charge fluctuation regime, showing excellent agreement with a recently introduced scheme based on a combination of numerical renormalization group with time-dependent density matrix renormalization group.

Prevalence of the geriatric syndromes and frailty in older men living in the community: The Concord Health and Ageing in Men Project.

PubMed

Noguchi, Naomi; Blyth, Fiona M; Waite, Louise M; Naganathan, Vasi; Cumming, Robert G; Handelsman, David J; Seibel, Markus J; Le Couteur, David G

2016-12-01

To describe the age at which the geriatric syndromes and frailty become common in community-dwelling men. The Concord Health and Ageing in Men Project involves a population-based sample of 1705 community-dwelling men aged 70 and over from a defined geographic region in Sydney. Data were obtained by physical performance tests, clinical examinations, and questionnaire to determine the prevalence of the following conditions by five-year age group. Poor mobility, recurrent falls, urinary incontinence, dementia and frailty phenotype were all uncommon (less than 10%) in men in their 70s, but the prevalence of each of these conditions exceeded 10% in men aged 85-89. The prevalence of Frailty Index-defined frailty, multimorbidity, polypharmacy and instrumental activities of daily living dependence was constantly high in all age groups. The different health-care needs of the 'old old' aged 85 years and older should be accounted for in health service planning. © 2016 AJA Inc.

The use of metalorganics in the preparation of semiconductor materials. VIII - Feasibility studies of the growth of Group III-Group V compounds of boron by MOCVD

NASA Technical Reports Server (NTRS)

Manasevit, H. M.; Hewitt, W. B.; Nelson, A. J.; Mason, A. R.

1989-01-01

The MOCVD growth of B-As and B-P films on Si, sapphire, and Si-on-sapphire substrates is described; in this process, trimethylborane (TMB) or triethylborane (TEB) is pyrolyzed in the presence of AsH3 or PH3 in an H2 atmosphere. The procedures employed are outlined, and the results are presented in graphs, tables, and micrographs. It is found that the growth rate of the primarily amorphous films is dependent on the TMB or TEB concentration but approximately constant for TEB and AsH3 at 550-900 C. The nominal compositions of films grown using TMB are given as B(12-16)As2 and B(1-1.3)P. Carbon impurities and significant stress, bowing, and crazing are observed in the films grown on Si substrates, with the highest carbon content in the films grown from TMB and PH3.

Renormalization group scale-setting from the action—a road to modified gravity theories

NASA Astrophysics Data System (ADS)

Domazet, Silvije; Štefančić, Hrvoje

2012-12-01

The renormalization group (RG) corrected gravitational action in Einstein-Hilbert and other truncations is considered. The running scale of the RG is treated as a scalar field at the level of the action and determined in a scale-setting procedure recently introduced by Koch and Ramirez for the Einstein-Hilbert truncation. The scale-setting procedure is elaborated for other truncations of the gravitational action and applied to several phenomenologically interesting cases. It is shown how the logarithmic dependence of the Newton's coupling on the RG scale leads to exponentially suppressed effective cosmological constant and how the scale-setting in particular RG-corrected gravitational theories yields the effective f(R) modified gravity theories with negative powers of the Ricci scalar R. The scale-setting at the level of the action at the non-Gaussian fixed point in Einstein-Hilbert and more general truncations is shown to lead to universal effective action quadratic in the Ricci tensor.

Model calibration and validation for OFMSW and sewage sludge co-digestion reactors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Esposito, G., E-mail: giovanni.esposito@unicas.it; Frunzo, L., E-mail: luigi.frunzo@unina.it; Panico, A., E-mail: anpanico@unina.it

2011-12-15

Highlights: > Disintegration is the limiting step of the anaerobic co-digestion process. > Disintegration kinetic constant does not depend on the waste particle size. > Disintegration kinetic constant depends only on the waste nature and composition. > The model calibration can be performed on organic waste of any particle size. - Abstract: A mathematical model has recently been proposed by the authors to simulate the biochemical processes that prevail in a co-digestion reactor fed with sewage sludge and the organic fraction of municipal solid waste. This model is based on the Anaerobic Digestion Model no. 1 of the International Watermore » Association, which has been extended to include the co-digestion processes, using surface-based kinetics to model the organic waste disintegration and conversion to carbohydrates, proteins and lipids. When organic waste solids are present in the reactor influent, the disintegration process is the rate-limiting step of the overall co-digestion process. The main advantage of the proposed modeling approach is that the kinetic constant of such a process does not depend on the waste particle size distribution (PSD) and rather depends only on the nature and composition of the waste particles. The model calibration aimed to assess the kinetic constant of the disintegration process can therefore be conducted using organic waste samples of any PSD, and the resulting value will be suitable for all the organic wastes of the same nature as the investigated samples, independently of their PSD. This assumption was proven in this study by biomethane potential experiments that were conducted on organic waste samples with different particle sizes. The results of these experiments were used to calibrate and validate the mathematical model, resulting in a good agreement between the simulated and observed data for any investigated particle size of the solid waste. This study confirms the strength of the proposed model and calibration procedure, which can thus be used to assess the treatment efficiency and predict the methane production of full-scale digesters.« less

C[subscript p]/C[subscript V] Ratios Measured by the Sound Velocity Method Using Calculator-Based Laboratory Technology

ERIC Educational Resources Information Center

Branca, Mario; Soletta, Isabella

2007-01-01

The velocity of sound in a gas depends on its temperature, molar mass, and [lambda] = C[subscript p]/C[subscript v], ratio (heat capacity at a constant pressure to heat capacity at constant volume). The [lambda] values for air, oxygen, nitrogen, argon, and carbon dioxide were determined by measuring the velocity of the sound through the gases at…

Binding constant of cell adhesion receptors and substrate-immobilized ligands depends on the distribution of ligands

NASA Astrophysics Data System (ADS)

Li, Long; Hu, Jinglei; Xu, Guangkui; Song, Fan

2018-01-01

Cell-cell adhesion and the adhesion of cells to tissues and extracellular matrix, which are pivotal for immune response, tissue development, and cell locomotion, depend sensitively on the binding constant of receptor and ligand molecules anchored on the apposing surfaces. An important question remains of whether the immobilization of ligands affects the affinity of binding with cell adhesion receptors. We have investigated the adhesion of multicomponent membranes to a flat substrate coated with immobile ligands using Monte Carlo simulations of a statistical mesoscopic model with biologically relevant parameters. We find that the binding of the adhesion receptors to ligands immobilized on the substrate is strongly affected by the ligand distribution. In the case of ligand clusters, the receptor-ligand binding constant can be significantly enhanced due to the less translational entropy loss of lipid-raft domains in the model cell membranes upon the formation of additional complexes. For ligands randomly or uniformly immobilized on the substrate, the binding constant is rather decreased since the receptors localized in lipid-raft domains have to pay an energetic penalty in order to bind ligands. Our findings help to understand why cell-substrate adhesion experiments for measuring the impact of lipid rafts on the receptor-ligand interactions led to contradictory results.

Effect of ripples on the finite temperature elastic properties of hexagonal boron nitride using strain-fluctuation method

NASA Astrophysics Data System (ADS)

Thomas, Siby; Ajith, K. M.; Valsakumar, M. C.

2017-11-01

This work intents to put forth the results of a classical molecular dynamics study to investigate the temperature dependent elastic constants of monolayer hexagonal boron nitride (h-BN) between 100 and 1000 K for the first time using strain fluctuation method. The temperature dependence of out-of-plane fluctuations (ripples) is quantified and is explained using continuum theory of membranes. At low temperatures, negative in-plane thermal expansion is observed and at high temperatures, a transition to positive thermal expansion has been observed due to the presence of thermally excited ripples. The decrease of Young's modulus, bulk modulus, shear modulus and Poisson's ratio with increase in temperature has been analyzed. The thermal rippling in h-BN leads to strong anharmonic behaviour that causes large deviation from the isotropic elasticity. A detailed study shows that the strong thermal rippling in large systems is also responsible for the softening of elastic constants in h-BN. From the determined values of elastic constants and elastic moduli, it has been elucidated that 2D h-BN sheets meet the Born's mechanical stability criterion in the investigated temperature range. The variation of longitudinal and shear velocities with temperature is also calculated from the computed values of elastic constants and elastic moduli.

Review of Slow-Wave Structures

NASA Technical Reports Server (NTRS)

Wallett, Thomas M.; Qureshi, A. Haq

1994-01-01

The majority of recent theoretical and experimental reports published in the literature dealing with helical slow-wave structures focus on the dispersion characteristics and their effects due to the finite helix wire thickness and attenuation, dielectric loading, metal loading, and the introduction of plasma. In many papers, an effective dielectric constant is used to take into account helix wire dimensions and conductivity losses, while the propagation constant of the signal and the interaction impedance of the structure are found to depend on the surface resistivity of the helix. Also, various dielectric supporting rods are simulated by one or several uniform cylinders having an effective dielectric constant, while metal vane loading and plasma effects are incorporated in the effective dielectric constant. The papers dealing with coupled cavities and folded or loaded wave guides describe equivalent circuit models, efficiency enhancement, and the prediction of instabilities for these structures. Equivalent circuit models of various structures are found using computer software programs SUPERFISH and TOUCHSTONE. Efficiency enhancement in tubes is achieved through dynamic velocity and phase adjusted tapers using computer techniques. The stability threshold of unwanted antisymmetric and higher order modes is predicted using SOS and MAGIC codes and the dependence of higher order modes on beam conductance, section length, and effective Q of a cavity is shown.

Radiation defect dynamics in Si at room temperature studied by pulsed ion beams

NASA Astrophysics Data System (ADS)

Wallace, J. B.; Charnvanichborikarn, S.; Bayu Aji, L. B.; Myers, M. T.; Shao, L.; Kucheyev, S. O.

2015-10-01

The evolution of radiation defects after the thermalization of collision cascades often plays the dominant role in the formation of stable radiation disorder in crystalline solids of interest to electronics and nuclear materials applications. Here, we explore a pulsed-ion-beam method to study defect interaction dynamics in Si crystals bombarded at room temperature with 500 keV Ne, Ar, Kr, and Xe ions. The effective time constant of defect interaction is measured directly by studying the dependence of lattice disorder, monitored by ion channeling, on the passive part of the beam duty cycle. The effective defect diffusion length is revealed by the dependence of damage on the active part of the beam duty cycle. Results show that the defect relaxation behavior obeys a second order kinetic process for all the cases studied, with a time constant in the range of ˜4-13 ms and a diffusion length of ˜15-50 nm. Both radiation dynamics parameters (the time constant and diffusion length) are essentially independent of the maximum instantaneous dose rate, total ion dose, and dopant concentration within the ranges studied. However, both the time constant and diffusion length increase with increasing ion mass. This demonstrates that the density of collision cascades influences not only defect production and annealing efficiencies but also the defect interaction dynamics.

Numerical calculations of temperature dependence of dielectric constant for an ordered assembly of BaTiO3 nanocubes with small tilt angles

NASA Astrophysics Data System (ADS)

Yasui, Kyuichi; Mimura, Ken-ichi; Izu, Noriya; Kato, Kazumi

2018-03-01

The dielectric constant of an ordered assembly of BaTiO3 nanocubes is numerically calculated as a function of temperature assuming a distribution of tilt angles of attached nanocubes. As the phase transition temperature from the tetragonal crystal structure to the cubic crystal structure of a BaTiO3 nanocube decreases as the tilt angle increases, the temperature at the peak of the dielectric constant of an ordered assembly is considerably lower than the Curie temperature of a free-standing BaTiO3 crystal. The peak of the dielectric constant as a function of temperature for an ordered assembly becomes considerably broader than that for a single crystal owing to the contribution of nanocubes with various tilt angles.

Ab initio perspective on the Mollwo-Ivey relation for F centers in alkali halides

NASA Astrophysics Data System (ADS)

Tiwald, Paul; Karsai, Ferenc; Laskowski, Robert; Gräfe, Stefanie; Blaha, Peter; Burgdörfer, Joachim; Wirtz, Ludger

2015-10-01

We revisit the well-known Mollwo-Ivey relation that describes the "universal" dependence of the absorption energies of F-type color centers on the lattice constant a of alkali-halide crystals, Eabs∝a-n. We perform both state-of-the-art ab initio quantum chemistry and post-DFT calculations of F-center absorption spectra. By "tuning" independently the lattice constant and the atomic species we show that the scaling with the lattice constant alone (keeping the elements fixed) would yield n =2 in agreement with the "particle-in-the-box" model. Keeping the lattice constant fixed and changing the atomic species enables us to quantify the ion-size effects which are shown to be responsible for the exponent n ≈1.8 .

Modification of the mean near-wall velocity profile of a high-Reynolds number turbulent boundary layer with the injection of drag-reducing polymer solutions

NASA Astrophysics Data System (ADS)

Elbing, Brian R.; Perlin, Marc; Dowling, David R.; Ceccio, Steven L.

2013-08-01

The current study explores the influence of polymer drag reduction on the near-wall velocity distribution in a turbulent boundary layer (TBL) and its dependence on Reynolds number. Recent moderate Reynolds number direct numerical simulation and experimental studies presented in White et al. [Phys. Fluids 24, 021701 (2012)], 10.1063/1.3681862 have challenged the classical representation of the logarithmic dependence of the velocity profile for drag-reduced flows, especially at drag reduction levels above 40%. In the present study, high Reynolds number data from a drag reduced TBL is presented and compared to the observations of White et al. [Phys. Fluids 24, 021701 (2012)], 10.1063/1.3681862. Data presented here were acquired in the TBL flow on a 12.9-m-long flat plate at speeds to 20.3 m s-1, achieving momentum thickness based Reynolds number to 1.5 × 105, which is an order of magnitude greater than that available in the literature. Polyethylene oxide solutions with an average molecular weight of 3.9 × 106 g mol-1 were injected into the flow at various concentrations and volumetric fluxes to achieve a particular level of drag reduction. The resulting mean near-wall velocity profiles show distinctly different behavior depending on whether they fall in the low drag reduction (LDR) or the high drag reduction (HDR) regimes, which are nominally divided at 40% drag reduction. In the LDR regime, the classical view that the logarithmic slope remains constant at the Newtonian value and the intercept constant increases with increasing drag reduction appears to be valid. However, in the HDR regime the behavior is no longer universal. The intercept constant continues to increase linearly in proportion to the drag reduction level until a Reynolds-number-dependent threshold is achieved, at which point the intercept constant rapidly decreases to that predicted by the ultimate profile. The rapid decrease in the intercept constant is due to the corresponding increase in the profile slope in the HDR regime. There was significant scatter in the observed slope in the HDR regime, but the scatter did not appear to be Reynolds number dependent. Finally, the ultimate profiles for flows at maximum drag reduction were examined and did not exhibit a logarithmic functional relationship, which is the classical empirical relationship suggested by Virk [J. Am. Inst. Chem. Eng. 21, 625-656 (1975)], 10.1002/aic.690210402.

Spinor Field Nonlinearity and Space-Time Geometry

NASA Astrophysics Data System (ADS)

Saha, Bijan

2018-03-01

Within the scope of Bianchi type VI,VI0,V, III, I, LRSBI and FRW cosmological models we have studied the role of nonlinear spinor field on the evolution of the Universe and the spinor field itself. It was found that due to the presence of non-trivial non-diagonal components of the energy-momentum tensor of the spinor field in the anisotropic space-time, there occur some severe restrictions both on the metric functions and on the components of the spinor field. In this report we have considered a polynomial nonlinearity which is a function of invariants constructed from the bilinear spinor forms. It is found that in case of a Bianchi type-VI space-time, depending of the sign of self-coupling constants, the model allows either late time acceleration or oscillatory mode of evolution. In case of a Bianchi VI 0 type space-time due to the specific behavior of the spinor field we have two different scenarios. In one case the invariants constructed from bilinear spinor forms become trivial, thus giving rise to a massless and linear spinor field Lagrangian. This case is equivalent to the vacuum solution of the Bianchi VI 0 type space-time. The second case allows non-vanishing massive and nonlinear terms and depending on the sign of coupling constants gives rise to accelerating mode of expansion or the one that after obtaining some maximum value contracts and ends in big crunch, consequently generating space-time singularity. In case of a Bianchi type-V model there occur two possibilities. In one case we found that the metric functions are similar to each other. In this case the Universe expands with acceleration if the self-coupling constant is taken to be a positive one, whereas a negative coupling constant gives rise to a cyclic or periodic solution. In the second case the spinor mass and the spinor field nonlinearity vanish and the Universe expands linearly in time. In case of a Bianchi type-III model the space-time remains locally rotationally symmetric all the time, though the isotropy of space-time can be attained for a large proportionality constant. As far as evolution is concerned, depending on the sign of coupling constant the model allows both accelerated and oscillatory mode of expansion. A negative coupling constant leads to an oscillatory mode of expansion, whereas a positive coupling constant generates expanding Universe with late time acceleration. Both deceleration parameter and EoS parameter in this case vary with time and are in agreement with modern concept of space-time evolution. In case of a Bianchi type-I space-time the non-diagonal components lead to three different possibilities. In case of a full BI space-time we find that the spinor field nonlinearity and the massive term vanish, hence the spinor field Lagrangian becomes massless and linear. In two other cases the space-time evolves into either LRSBI or FRW Universe. If we consider a locally rotationally symmetric BI( LRSBI) model, neither the mass term nor the spinor field nonlinearity vanishes. In this case depending on the sign of coupling constant we have either late time accelerated mode of expansion or oscillatory mode of evolution. In this case for an expanding Universe we have asymptotical isotropization. Finally, in case of a FRW model neither the mass term nor the spinor field nonlinearity vanishes. Like in LRSBI case we have either late time acceleration or cyclic mode of evolution. These findings allow us to conclude that the spinor field is very sensitive to the gravitational one.

Computational scheme for pH-dependent binding free energy calculation with explicit solvent.

PubMed

Lee, Juyong; Miller, Benjamin T; Brooks, Bernard R

2016-01-01

We present a computational scheme to compute the pH-dependence of binding free energy with explicit solvent. Despite the importance of pH, the effect of pH has been generally neglected in binding free energy calculations because of a lack of accurate methods to model it. To address this limitation, we use a constant-pH methodology to obtain a true ensemble of multiple protonation states of a titratable system at a given pH and analyze the ensemble using the Bennett acceptance ratio (BAR) method. The constant pH method is based on the combination of enveloping distribution sampling (EDS) with the Hamiltonian replica exchange method (HREM), which yields an accurate semi-grand canonical ensemble of a titratable system. By considering the free energy change of constraining multiple protonation states to a single state or releasing a single protonation state to multiple states, the pH dependent binding free energy profile can be obtained. We perform benchmark simulations of a host-guest system: cucurbit[7]uril (CB[7]) and benzimidazole (BZ). BZ experiences a large pKa shift upon complex formation. The pH-dependent binding free energy profiles of the benchmark system are obtained with three different long-range interaction calculation schemes: a cutoff, the particle mesh Ewald (PME), and the isotropic periodic sum (IPS) method. Our scheme captures the pH-dependent behavior of binding free energy successfully. Absolute binding free energy values obtained with the PME and IPS methods are consistent, while cutoff method results are off by 2 kcal mol(-1) . We also discuss the characteristics of three long-range interaction calculation methods for constant-pH simulations. © 2015 The Protein Society.

Modeling the influence of preferential flow on the spatial variability and time-dependence of mineral weathering rates

DOE PAGES

Pandey, Sachin; Rajaram, Harihar

2016-12-05

Inferences of weathering rates from laboratory and field observations suggest significant scale and time-dependence. Preferential flow induced by heterogeneity (manifest as permeability variations or discrete fractures) has been suggested as one potential mechanism causing scale/time-dependence. In this paper, we present a quantitative evaluation of the influence of preferential flow on weathering rates using reactive transport modeling. Simulations were performed in discrete fracture networks (DFNs) and correlated random permeability fields (CRPFs), and compared to simulations in homogeneous permeability fields. The simulations reveal spatial variability in the weathering rate, multidimensional distribution of reactions zones, and the formation of rough weathering interfaces andmore » corestones due to preferential flow. In the homogeneous fields and CRPFs, the domain-averaged weathering rate is initially constant as long as the weathering front is contained within the domain, reflecting equilibrium-controlled behavior. The behavior in the CRPFs was influenced by macrodispersion, with more spread-out weathering profiles, an earlier departure from the initial constant rate and longer persistence of weathering. DFN simulations exhibited a sustained time-dependence resulting from the formation of diffusion-controlled weathering fronts in matrix blocks, which is consistent with the shrinking core mechanism. A significant decrease in the domain-averaged weathering rate is evident despite high remaining mineral volume fractions, but the decline does not follow a math formula dependence, characteristic of diffusion, due to network scale effects and advection-controlled behavior near the inflow boundary. Finally, the DFN simulations also reveal relatively constant horizontally averaged weathering rates over a significant depth range, challenging the very notion of a weathering front.« less