Soret and Dufour effects on MHD peristaltic flow of Prandtl fluid in a rotating channel

NASA Astrophysics Data System (ADS)

Hayat, Tasawar; Zahir, Hina; Tanveer, Anum; Alsaedi, Ahmed

2018-03-01

An analysis has been arranged to study the magnetohydrodynamics (MHD) peristaltic flow of Prandtl fluid in a channel with flexible walls. Both fluid and channel are in a state of solid body rotation. Simultaneous effects of heat and mass transfer with thermal-diffusion (Soret) and diffusion-thermo (Dufour) effects are considered. Convective conditions for heat and mass transfer in the formulation are adopted. Ordinary differential systems using low Reynolds number and long wavelength approximation are obtained. Resulting equations have been solved numerically. The discussion of axial and secondary velocities, temperature, concentration and heat transfer coefficient with respect to emerging parameters embedded in the flow model is presented after sketching plots.

Soret motion in non-ionic binary molecular mixtures

NASA Astrophysics Data System (ADS)

Leroyer, Yves; Würger, Alois

2011-08-01

We study the Soret coefficient of binary molecular mixtures with dispersion forces. Relying on standard transport theory for liquids, we derive explicit expressions for the thermophoretic mobility and the Soret coefficient. Their sign depends on composition, the size ratio of the two species, and the ratio of Hamaker constants. Our results account for several features observed in experiment, such as a linear variation with the composition; they confirm the general rule that small molecules migrate to the warm, and large ones to the cold.

Thermophoresis of a Brownian particle driven by inhomogeneous thermal fluctuation

NASA Astrophysics Data System (ADS)

Tsuji, Tetsuro; Saita, Sho; Kawano, Satoyuki

2018-03-01

Brownian motion of a spherical particle induced by the interaction with surrounding molecules is considered. If the particle is larger than the molecules and the temperature of surrounding media is spatially non-uniform, the interaction between an individual molecule and the particle is also position-dependent. That is, the particle is subject to inhomogeneous thermal fluctuation. In this paper, we investigate the contribution of the inhomogeneous thermal fluctuation to the thermophoresis, i.e., the Soret coefficient or thermal diffusion factor. The problem is simplified by assuming a hard-sphere potential between the particle and the surrounding molecules and is investigated using the kinetic theory, namely, we consider a linear Boltzmann-type equation for the velocity distribution function of the particle. Using the perturbation analysis with respect to the square root of mass ratio between the molecule and the particle, the drift-diffusion equation of the particle is derived. It is found that the Soret coefficient, or thermal diffusion factor, is dependent on the mass ratio and the excluded volume of the particle. In particular, when the ratio of the mass density of the particle to that of the surrounding media decreases, the Soret coefficient also decreases and may take negative value. The present result well describes the mass-dependency of thermal diffusion factor obtained by the molecular dynamics simulation carried out in an existing study and the one in the present study, where soft potentials of Lennard-Jones-type are used instead of hard-sphere potential.

Thermal diffusion behavior of hard-sphere suspensions.

PubMed

Ning, Hui; Buitenhuis, Johan; Dhont, Jan K G; Wiegand, Simone

2006-11-28

We studied the thermal diffusion behavior of octadecyl coated silica particles (R(h)=27 nm) in toluene between 15.0 and 50.0 degrees C in a volume fraction range of 1%-30% by means of thermal diffusion forced Rayleigh scattering. The colloidal particles behave like hard spheres at high temperatures and as sticky spheres at low temperatures. With increasing temperature, the obtained Soret coefficient S(T) of the silica particles changed sign from negative to positive, which implies that the colloidal particles move to the warm side at low temperatures, whereas they move to the cold side at high temperatures. Additionally, we observed also a sign change of the Soret coefficient from positive to negative with increasing volume fraction. This is the first colloidal system for which a sign change with temperature and volume fraction has been observed. The concentration dependence of the thermal diffusion coefficient of the colloidal spheres is related to the colloid-colloid interactions, and will be compared with an existing theoretical description for interacting spherical particles. To characterize the particle-particle interaction parameters, we performed static and dynamic light scattering experiments. The temperature dependence of the thermal diffusion coefficient is predominantly determined by single colloidal particle properties, which are related to colloid-solvent molecule interactions.

Light-induced thermodiffusion in two-component media

NASA Astrophysics Data System (ADS)

Ivanov, V.; Ivanova, G.; Okishev, K.; Khe, V.

2017-01-01

We have theoretically studied the optical transmittance response of thin cell with liquid containing absorbing nanoparticles in a Gaussian beam field. The transmittance spatial changing is caused by thermal diffusion phenomenon (Soret effect) which produces the variations of concentration of absorbing nanoparticles. The thickness of optical cell (including windows) is significantly less than the size of the beam. As a result, an exact analytical expression for the one dimensional thermal task is derived, taking into account the Soret feedback that leads to the temperature rising on the axis of a Gaussian beam. We have experimentally studied this phenomenon in carbon nanosuspension.

CWIS Experiment On Board REXUS-16 Sounding Rocket: Investigation of the Chemical Wave in Binary Mixture

NASA Astrophysics Data System (ADS)

Tzevelecos, W.; Pugliese, A.; de Filippis, L.; Manzone, S.; Alfano, B.; Mancino, F.; Runge, W.; Desenfans, O.; Galand, Q.; Van Vaerenbergh, S.

2015-09-01

Chemical Wave in Soret Effect (CWIS) is an experiment launched in May 2014 on-board a REXUS sounding rocket from Esrange Space Center. The experiment was completely designed and assembled by students from different countries under an international collaboration between the Université libre de Bruxelles (ULB) and the University of Naples Federico II. This student program called REXUS/BEXUS allows students to perform experiments in space science applications under the supervision of the European Space Agency (ESA). The objective of the CWIS Team was to visualize the Chemical Wave (CW) during the transient of the Soret effect. The CW is a concentration front that rapidly propagates under thermal gradient in a liquid mixture, and which marks the beginning of the chemical separation phenomenon by thermodiffusion (the separation process is itself named Soret effect, but is usually analyzed statically). The selected mixture was a solution of Ethylene Glycol in Water and concentration variation due to thermal gradients was recorded using a modified Fizeau interferometer, with modifications designed to enlarge a very small region of the test cell using cylindrical squeezing. We recorded more than 100 images with the chemical information and in this paper work we will show the final results of the sounding rocket experiment.

The first TDDFT and MCD studies of free base triarylcorroles: a closer look into solvent-dependent UV-visible absorption.

PubMed

Ziegler, Christopher J; Sabin, Jared R; Geier, G Richard; Nemykin, Victor N

2012-05-16

Absorption spectra of several free base triarylcorroles were investigated by MCD spectroscopy. The MCD spectra exhibit unusual sign-reverse (positive-to-negative intensities in ascending energy) features in the Soret- and Q-type band regions, suggesting a rare ΔHOMO < ΔLUMO relationship between π and π* MOs in the corrole core. This journal is © The Royal Society of Chemistry 2012

Ultrafast relaxation dynamics of nitric oxide synthase studied by visible broadband transient absorption spectroscopy

NASA Astrophysics Data System (ADS)

Hung, Chih-Chang; Yabushita, Atsushi; Kobayashi, Takayoshi; Chen, Pei-Feng; Liang, Keng S.

2017-09-01

Ultrafast dynamics of endothelial nitric oxide synthase (eNOS) oxygenase domain was studied by transient absorption spectroscopy pumping at Soret band. The broadband visible probe spectrum has visualized the relaxation dynamics from the Soret band to Q-band and charge transfer (CT) band. Supported by two-dimensional correlation spectroscopy, global fitting analysis has successfully concluded the relaxation dynamics from the Soret band to be (1) electronic transition to Q-band (0.16 ps), (2) ligand dissociation and CT (0.94 ps), (3) relaxation of the CT state (4.0 ps), and (4) ligand rebinding (59 ps).

Mathematical analysis of thermal diffusion shock waves

NASA Astrophysics Data System (ADS)

Gusev, Vitalyi; Craig, Walter; Livoti, Roberto; Danworaphong, Sorasak; Diebold, Gerald J.

2005-10-01

Thermal diffusion, also known as the Ludwig-Soret effect, refers to the separation of mixtures in a temperature gradient. For a binary mixture the time dependence of the change in concentration of each species is governed by a nonlinear partial differential equation in space and time. Here, an exact solution of the Ludwig-Soret equation without mass diffusion for a sinusoidal temperature field is given. The solution shows that counterpropagating shock waves are produced which slow and eventually come to a halt. Expressions are found for the shock time for two limiting values of the starting density fraction. The effects of diffusion on the development of the concentration profile in time and space are found by numerical integration of the nonlinear differential equation.

Influence of Soret-Dufour and thermophoresis on hydromagnetic mixed convection heat and mass transfer over an inclined flat plate with non-uniform heat source/sink and chemical reaction

NASA Astrophysics Data System (ADS)

Pal, Dulal; Mondal, Hiranmoy

2018-03-01

The paper is devoted to the study of thermophoresis and Soret-Dufour effects on magnetohydrodynamic mixed convective heat and mass transfer over an inclined flat plate with non-uniform heat source/sink. Governing non-linear coupled ordinary differential equations are solved numerically using Runge-Kutta Fehlberg technique with shooting scheme. The effects of various physical parameters on the velocity, temperature, and concentration profiles are depicted graphically. The values of skin-friction coefficient, Nusselt number and Sherwood number are presented in a tabular form. It is found that increase in thermophoretic and chemical reaction parameters retard the velocity and concentration distributions in the boundary layer.

Measurement of Soret and Fickian diffusion coefficients by orthogonal phase-shifting interferometry and its application to protein aqueous solutions

NASA Astrophysics Data System (ADS)

Torres, Juan F.; Komiya, Atsuki; Henry, Daniel; Maruyama, Shigenao

2013-08-01

We have developed a method to measure thermodiffusion and Fickian diffusion in transparent binary solutions. The measuring instrument consists of two orthogonally aligned phase-shifting interferometers coupled with a single rotating polarizer. This high-resolution interferometer, initially developed to measure isothermal diffusion coefficients in liquid systems [J. F. Torres, A. Komiya, E. Shoji, J. Okajima, and S. Maruyama, Opt. Lasers Eng. 50, 1287 (2012)], was modified to measure transient concentration profiles in binary solutions subject to a linear temperature gradient. A convectionless thermodiffusion field was created in a binary solution sample that is placed inside a Soret cell. This cell consists of a parallelepiped cavity with a horizontal cross-section area of 10 × 20 mm2, a variable height of 1-2 mm, and transparent lateral walls. The small height of the cell reduces the volume of the sample, shortens the measurement time, and increases the hydrodynamic stability of the system. An additional free diffusion experiment with the same optical apparatus provides the so-called contrast factors that relate the unwrapped phase and concentration gradients, i.e., the measurement technique is independent and robust. The Soret coefficient is determined from the concentration and temperature differences between the upper and lower boundaries measured by the interferometer and thermocouples, respectively. The Fickian diffusion coefficient is obtained by fitting a numerical solution to the experimental concentration profile. The method is validated through the measurement of thermodiffusion in the well-known liquid pairs of ethanol-water (ethanol 39.12 wt.%) and isobutylbenzene-dodecane (50.0 wt.%). The obtained coefficients agree with the literature values within 5.0%. Finally, the developed technique is applied to visualize biomolecular thermophoresis. Two protein aqueous solutions at 3 mg/ml were used as samples: aprotinin (6.5 kDa)-water and lysozyme (14.3 kDa)-water. It was found that the former protein molecules are thermophilic and the latter thermophobic. In contrast to previously reported methods, this technique is suitable for both short time and negative Soret coefficient measurements.

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

Arias-Zugasti, Manuel; High Temperature Chemical Reaction Engineering Laboratory and Yale Center for Combustion Studies, Department of Chemical Engineering, Yale University, New Haven, CT 06520-8286; Rosner, Daniel E.

Since, according to ideal gas kinetic theory, Ludwig-Soret species transport (temperature-gradient-driven mass transport) must be simultaneously included along with nonunity Lewis numbers [D.E. Rosner, R.S. Israel, B. La Mantia, Combust. Flame 123 (2000) 547-560], we formally consider here the influence of both effects on laminar, counterflow gaseous diffusion flames in the thin flame limit. Our deliberately idealized theoretical analysis includes cases of steady/unsteady, strained/unstrained flames and formally permits the prediction of trends for the combustion of either light or heavy fuel vapors in O{sub 2}-containing streams. Our results suggest that, in cases of low- or high-molecular-weight gaseous fuels, Ludwig-Soret transportmore » can itself introduce significant shifts in flame position and flame temperature, compared to results of the same mathematical model neglecting Soret fuel-vapor transport but including only nonunity fuel Lewis numbers. These systematic shifts (which in specific cases may have to be supplemented by additional corrections due to variable thermophysical properties) are expected to have important consequences for NO{sub x} production and/or infrared radiation emission. (author)« less

Dissipative slip flow along heat and mass transfer over a vertically rotating cone by way of chemical reaction with Dufour and Soret effects

NASA Astrophysics Data System (ADS)

Bilal, S.; Rehman, Khalil Ur; Jamil, Hamayun; Malik, M. Y.; Salahuddin, T.

2016-12-01

An attempt has been constructed in the communication to envision heat and mass transfer characteristics of viscous fluid over a vertically rotating cone. Thermal transport in the fluid flow is anticipated in the presence of viscous dissipation. Whereas, concentration of fluid particles is contemplated by incorporating the diffusion-thermo (Dufour) and thermo-diffusion (Soret) effects. The governing equations for concerning problem is first modelled and then nondimensionalized by implementing compatible transformations. The utilization of these transformations yields ordinary differential system which is computed analytically through homotopic procedure. Impact of velocity, temperature and concentration profiles are presented through fascinating graphics. The influence of various pertinent parameters on skin friction coefficient, Nusselt number and Sherwood number are interpreted through graphical and tabular display. After comprehensive examination of analysis, it is concluded that temperature of fluid deescalates for growing values of Soret parameter whereas it shows inciting attitude towards Dufour parameter and similar agreement is observed for the behavior of concentration profile with respect to these parameters. Furthermore, the affirmation of present work is established by developing comparison with previously published literature. An excellent agreement is found which shows the credibility and assurance of present analysis.

Hydrodynamic Boundary Effects on Thermophoresis of Confined Colloids.

PubMed

Würger, Alois

2016-04-01

We study hydrodynamic slowing down of a particle moving in a temperature gradient perpendicular to a wall. At distances much smaller than the particle radius, h≪a, the lubrication approximation leads to the reduced velocity u/u_{0}=3(h/a)[ln(a/h)-9/4], where u_{0} is the velocity in the bulk. With Brenner's result for confined diffusion, we find that the trapping efficiency, or effective Soret coefficient, increases logarithmically as the particle gets very close to the wall. Our results provide a quantitative explanation for the recently observed enhancement of thermophoretic trapping at short distances. Our discussion of parallel and perpendicular thermophoresis in a capillary reveals a good agreement with experiments on charged polystyrene particles, and sheds some light on a controversy concerning the size dependence and the nonequilibrium nature of the Soret effect.

Linear temporal and spatio-temporal stability analysis of a binary liquid film flowing down an inclined uniformly heated plate

NASA Astrophysics Data System (ADS)

Hu, Jun; Hadid, Hamda Ben; Henry, Daniel; Mojtabi, Abdelkader

Temporal and spatio-temporal instabilities of binary liquid films flowing down an inclined uniformly heated plate with Soret effect are investigated by using the Chebyshev collocation method to solve the full system of linear stability equations. Seven dimensionless parameters, i.e. the Kapitza, Galileo, Prandtl, Lewis, Soret, Marangoni, and Biot numbers (Ka, G, Pr, L, ) are used to control the flow system. In the case of pure spanwise perturbations, thermocapillary S- and P-modes are obtained. It is found that the most dangerous modes are stationary for positive Soret numbers (0), and oscillatory for =0 remains so for >0 and even merges with the long-wave S-mode. In the case of streamwise perturbations, a long-wave surface mode (H-mode) is also obtained. From the neutral curves, it is found that larger Soret numbers make the film flow more unstable as do larger Marangoni numbers. The increase of these parameters leads to the merging of the long-wave H- and S-modes, making the situation long-wave unstable for any Galileo number. It also strongly influences the short-wave P-mode which becomes the most critical for large enough Galileo numbers. Furthermore, from the boundary curves between absolute and convective instabilities (AI/CI) calculated for both the long-wave instability (S- and H-modes) and the short-wave instability (P-mode), it is shown that for small Galileo numbers the AI/CI boundary curves are determined by the long-wave instability, while for large Galileo numbers they are determined by the short-wave instability.

Excitation energy transfer from the bacteriochlorophyll Soret band to carotenoids in the LH2 light-harvesting complex from Ectothiorhodospira haloalkaliphila is negligible.

PubMed

Razjivin, A P; Lukashev, E P; Kompanets, V O; Kozlovsky, V S; Ashikhmin, A A; Chekalin, S V; Moskalenko, A A; Paschenko, V Z

2017-09-01

Pathways of intramolecular conversion and intermolecular electronic excitation energy transfer (EET) in the photosynthetic apparatus of purple bacteria remain subject to debate. Here we experimentally tested the possibility of EET from the bacteriochlorophyll (BChl) Soret band to the singlet S 2 level of carotenoids using femtosecond pump-probe measurements and steady-state fluorescence excitation and absorption measurements in the near-ultraviolet and visible spectral ranges. The efficiency of EET from the Soret band of BChl to S 2 of the carotenoids in light-harvesting complex LH2 from the purple bacterium Ectothiorhodospira haloalkaliphila appeared not to exceed a few percent.

Influence of temperature and charge effects on thermophoresis of polystyrene beads⋆.

PubMed

Syshchyk, Olga; Afanasenkau, Dzmitry; Wang, Zilin; Kriegs, Hartmut; Buitenhuis, Johan; Wiegand, Simone

2016-12-01

We study the thermodiffusion behavior of spherical polystyrene beads with a diameter of 25 nm by infrared thermal diffusion Forced Rayleigh Scattering (IR-TDFRS). Similar beads were used to investigate the radial dependence of the Soret coefficient by different authors. While Duhr and Braun (Proc. Natl. Acad. Sci. U.S.A. 104, 9346 (2007)) observed a quadratic radial dependence Braibanti et al. (Phys. Rev. Lett. 100, 108303 (2008)) found a linear radial dependence of the Soret coefficient. We demonstrated that special care needs to be taken to obtain reliable thermophoretic data, because the measurements are very sensitive to surface properties. The colloidal particles were characterized by transmission electron microscopy and dynamic light scattering (DLS) experiments were performed. We carried out systematic thermophoretic measurements as a function of temperature, buffer and surfactant concentration. The temperature dependence was analyzed using an empirical formula. To describe the Debye length dependence we used a theoretical model by Dhont. The resulting surface charge density is in agreement with previous literature results. Finally, we analyze the dependence of the Soret coefficient on the concentration of the anionic surfactant sodium dodecyl sulfate (SDS), applying an empirical thermodynamic approach accounting for chemical contributions.

Colloidal motion under the action of a thermophoretic force.

PubMed

Burelbach, Jerome; Zupkauskas, Mykolas; Lamboll, Robin; Lan, Yang; Eiser, Erika

2017-09-07

We present thermophoretic measurements in aqueous suspensions of three different polystyrene (PS) particles of varying negative charge, size, and surface coating. Our measurement technique is based on the observation of the colloidal steady-state distribution using conventional bright-field microscopy, which avoids undesirable effects such as laser-induced convection or local heating. We find that the colloids with the weakest zeta potential exhibit the strongest thermophoretic effect, suggesting that the Soret coefficient has a more intricate dependence on surface functionality than predicted by existing theoretical approaches. We also study the relaxation of the colloids to steady-state and propose a model to quantify the relaxation speed, based on the time evolution of the colloidal center of mass. Our observations are well described by this model and show that the relaxation speed tends to increase with the magnitude of the thermophoretic force.

Colloidal motion under the action of a thermophoretic force

NASA Astrophysics Data System (ADS)

Burelbach, Jerome; Zupkauskas, Mykolas; Lamboll, Robin; Lan, Yang; Eiser, Erika

2017-09-01

We present thermophoretic measurements in aqueous suspensions of three different polystyrene (PS) particles of varying negative charge, size, and surface coating. Our measurement technique is based on the observation of the colloidal steady-state distribution using conventional bright-field microscopy, which avoids undesirable effects such as laser-induced convection or local heating. We find that the colloids with the weakest zeta potential exhibit the strongest thermophoretic effect, suggesting that the Soret coefficient has a more intricate dependence on surface functionality than predicted by existing theoretical approaches. We also study the relaxation of the colloids to steady-state and propose a model to quantify the relaxation speed, based on the time evolution of the colloidal center of mass. Our observations are well described by this model and show that the relaxation speed tends to increase with the magnitude of the thermophoretic force.

Time-dependent patterns in quasivertical cylindrical binary convection.

PubMed

Alonso, Arantxa; Mercader, Isabel; Batiste, Oriol

2018-02-01

This paper reports on numerical investigations of the effect of a slight inclination α on pattern formation in a shallow vertical cylindrical cell heated from below for binary mixtures with a positive value of the Soret coefficient. By using direct numerical simulation of the three-dimensional Boussinesq equations with Soret effect in cylindrical geometry, we show that a slight inclination of the cell in the range α≈0.036rad=2^{∘} strongly influences pattern selection. The large-scale shear flow (LSSF) induced by the small tilt of gravity overcomes the squarelike arrangements observed in noninclined cylinders in the Soret regime, stratifies the fluid along the direction of inclination, and produces an enhanced separation of the two components of the mixture. The competition between shear effects and horizontal and vertical buoyancy alters significantly the dynamics observed in noninclined convection. Additional unexpected time-dependent patterns coexist with the basic LSSF. We focus on an unsual periodic state recently discovered in an experiment, the so-called superhighway convection state (SHC), in which ascending and descending regions of fluid move in opposite directions. We provide numerical confirmation that Boussinesq Navier-Stokes equations with standard boundary conditions contain the essential ingredients that allow for the existence of such a state. Also, we obtain a persistent heteroclinic structure where regular oscillations between a SHC pattern and a state of nearly stationary longitudinal rolls take place. We characterize numerically these time-dependent patterns and investigate the dynamics around the threshold of convection.

Time-dependent patterns in quasivertical cylindrical binary convection

NASA Astrophysics Data System (ADS)

Alonso, Arantxa; Mercader, Isabel; Batiste, Oriol

2018-02-01

This paper reports on numerical investigations of the effect of a slight inclination α on pattern formation in a shallow vertical cylindrical cell heated from below for binary mixtures with a positive value of the Soret coefficient. By using direct numerical simulation of the three-dimensional Boussinesq equations with Soret effect in cylindrical geometry, we show that a slight inclination of the cell in the range α ≈0.036 rad =2∘ strongly influences pattern selection. The large-scale shear flow (LSSF) induced by the small tilt of gravity overcomes the squarelike arrangements observed in noninclined cylinders in the Soret regime, stratifies the fluid along the direction of inclination, and produces an enhanced separation of the two components of the mixture. The competition between shear effects and horizontal and vertical buoyancy alters significantly the dynamics observed in noninclined convection. Additional unexpected time-dependent patterns coexist with the basic LSSF. We focus on an unsual periodic state recently discovered in an experiment, the so-called superhighway convection state (SHC), in which ascending and descending regions of fluid move in opposite directions. We provide numerical confirmation that Boussinesq Navier-Stokes equations with standard boundary conditions contain the essential ingredients that allow for the existence of such a state. Also, we obtain a persistent heteroclinic structure where regular oscillations between a SHC pattern and a state of nearly stationary longitudinal rolls take place. We characterize numerically these time-dependent patterns and investigate the dynamics around the threshold of convection.

The onset of convection in a binary fluid mixture with temperature dependent viscosity and Coriolis force with Soret presence

NASA Astrophysics Data System (ADS)

Abidin, Nurul Hafizah Zainal; Mokhtar, Nor Fadzillah Mohd; Majid, Zanariah Abdul; Ghani, Siti Salwa Abd

2017-11-01

Temperature dependent viscosity and Coriolis force were applied to the steady Benard-Marangoni convection where the lower boundary of a horizontal layer of the binary mixture is heated from below and cooled from above. The purpose of this paper is to study in detail the onset of convection with these effects. Few cases of boundary conditions are studied which are rigid-rigid, rigid-free and free-free representing the lower-upper boundaries. A detailed numerical calculation of the marginal stability curves was performed by using the Galerkin method and it is showed that temperature dependent viscosity and Soret number destabilize the binary fluid layer system and Taylor number act oppositely.

Vibration effect on the Soret-induced convection of ternary mixture in a rectangular cavity heated from below

NASA Astrophysics Data System (ADS)

Lyubimova, T. P.; Zubova, N. A.

2017-06-01

This paper presents the results of numerical simulation of the Soret-induced convection of ternary mixture in the rectangular cavity elongated in horizontal direction in gravity field. The cavity has rigid impermeable boundaries. It is heated from the bellow and undergoes translational linearly polarized vibrations of finite amplitude and frequency in the horizontal direction. The problem is solved by finite difference method in the framework of full unsteady non-linear approach. The procedure of diagonalization of the molecular diffusion coefficient matrix is applied, allowing to eliminate cross-diffusion components in the equations and to reduce the number of the governing parameters. The calculations are performed for model ternary mixture with positive separation ratios of the components. The data on the vibration effect on temporal evolution of instantaneous and average fields and integral characteristics of the flow and heat and mass transfer at different levels of gravity are obtained.

Three-dimensional convection of binary mixtures in porous media.

PubMed

Umla, R; Augustin, M; Huke, B; Lücke, M

2011-11-01

We investigate convection patterns of binary mixtures with a positive separation ratio in porous media. As setup, we choose the Rayleigh-Bénard system of a fluid layer heated from below. Results are obtained by a multimode Galerkin method. Using this method, we compute square and crossroll patterns, and we analyze their structural, bifurcation, and stability properties. Evidence is provided that, for a strong enough Soret effect, both structures exist as stable forms of convection. Some of their properties are found to be similar to square and crossroll convection in the system without porous medium. However, there are also qualitative differences. For example, squares can be destabilized by oscillatory perturbations with square symmetry in porous media, and their velocity isolines are deformed in the so-called Soret regime.

Transient-state method for coupled evaluation of Soret and Fick coefficients, and related tortuosity factors, using free and porous packed thermodiffusion cells: application to CuSO4 aqueous solution ( 0.25M).

PubMed

Costesèque, P; Pollak, T; Platten, J K; Marcoux, M

2004-11-01

The measurement of Soret coefficients in liquids is not easy and usually not very precise because the resulting concentration gradient is small and moreover can be perturbed by undesired convection currents. In order to suppress, or to drastically reduce these convection currents, the use of a porous medium is sometimes suggested. The question arises as to whether the Soret coefficient is the same in free fluid and in porous medium. This is the aim of this paper. To this end, for a given liquid mixture, the time evolution of the vertical concentration gradient is experimentally measured in the same thermodiffusion cell filled first with the free liquid and next with a porous medium followed by saturation by the liquid mixture. Both the isothermal diffusion (Fick) coefficient and the Soret coefficient can be deduced, providing that a correct working equation is used. The proposed equation results from integration of the general mass conservation equation with realistic boundary conditions (zero mass flux at the boundaries) and some simplifying assumptions rendering this equation more tractable than the one proposed some decades ago by Bierlein (J.A. Bierlein, J. Chem. Phys. 23, 10 (1955)). The method is applied here to an electrolytic solution (CuSO4, 0.25 M) at a mean temperature of 37 degrees C. The Soret coefficients in free and porous medium (zircon microspheres in the range of 250-315 x 10(-6) m) may be considered to be equal ( S(T) = 13.2+/-0.5 x 10(-3) K(-1)) and the tortuosity factors for the packed medium are the same relative to thermodiffusion and Fick coefficients (tau = 1.51+/-0.02).

Combined Influence of Hall Current and Soret Effect on Chemically Reacting Magnetomicropolar Fluid Flow from Radiative Rotating Vertical Surface with Variable Suction in Slip-Flow Regime

PubMed Central

Jain, Preeti

2014-01-01

An analysis study is presented to study the effects of Hall current and Soret effect on unsteady hydromagnetic natural convection of a micropolar fluid in a rotating frame of reference with slip-flow regime. A uniform magnetic field acts perpendicularly to the porous surface which absorbs the micropolar fluid with variable suction velocity. The effects of heat absorption, chemical reaction, and thermal radiation are discussed and for this Rosseland approximation is used to describe the radiative heat flux in energy equation. The entire system rotates with uniform angular velocity Ω about an axis normal to the plate. The nonlinear coupled partial differential equations are solved by perturbation techniques. In order to get physical insight, the numerical results of translational velocity, microrotation, fluid temperature, and species concentration for different physical parameters entering into the analysis are discussed and explained graphically. Also, the results of the skin-friction coefficient, the couple stress coefficient, Nusselt number, and Sherwood number are discussed with the help of figures for various values of flow pertinent flow parameters. PMID:27350957

Absorption Peaks: α, β, γ and Their Covariance with Age and Hemoglobin in Human Blood Samples Using Photoacoustic Spectroscopy

NASA Astrophysics Data System (ADS)

González-Domínguez, J. L.; Hernández-Aguilar, C.; Domínguez-Pacheco, F. A.; Martínez-Ortiz, E.; Cruz-Orea, A.; Sánchez-Sinencio, F.

2012-11-01

This study reports the absorption peaks α, β, γ in the Soret band of photoacoustic (PA) signals and their covariance with age and hemoglobin in human blood samples through PA spectroscopy. Samples were taken randomly from a masculine population grouped in three categories according to age: infants, young adults, and senior adults. Samples were prepared with two drops of blood from a 0.5 mL insulin syringe with a needle gauge 31G over 5 mm circles of filter paper. It was observed that the PA signal, the amplitude as a function of the wavelength, has a behavior as that reported for human blood for the three absorption peaks α, β, γ. In particular, the ratio γ/ β is due to electronic transitions associated with charge-transfer interactions of iron orbitals with the ligand states. Through an evaluation of optical absorption peaks in blood samples and their covariance with age and hemoglobin concentration, a relationship was found for the ratio peaks γ/ β and γ/ α with such parameters. Specifically, a negative covariance in the Soret band of the ratio peaks γ/ β and γ/ α with respect to both age and hemoglobin was found. This showed a tendency in their behavior. Further experiments of different populations may corroborate these conclusions.

Photophysics of Zinc Porphyrin Aggregates in Dilute Water-Ethanol Solutions.

PubMed

Stevens, Amy L; Joshi, Neeraj K; Paige, Matthew F; Steer, Ronald P

2017-12-14

Dimeric and multimeric aggregates of a model metalloporphyrin, zinc tetraphenylporphyrin (ZnTPP), have been produced in a controlled manner by incrementally increasing the water content of dilute aqueous ethanol solutions. Steady state absorption, fluorescence emission, and fluorescence excitation spectra have been measured to identify the aggregates present as a function of solvent composition. The dynamics of the excited states of the aggregates produced initially by excitation in the Soret region have been measured by ultrafast fluorescence upconversion techniques. Only the monomer produces measurable emission from S 2 with a picosecond lifetime; all Soret-excited aggregates, including the dimer, decay radiationlessly on a femtosecond time scale. The S 1 state is the only significant product of the radiationless decay of the S 2 state of the excited monomer, and the aggregates also produce substantial quantum yields of S 1 fluorescence when initially excited in the Soret region. The resulting fluorescent aggregates all decay on a subnanosecond time scale, likely by a mechanism that involves dissociation of the excited monomer from the excitonic multimer. The ZnTPP dimers excited at their ground state geometries in the Soret region exhibit a dynamic behavior that is quite different from those produced following noncoherent triplet-triplet annihilation under the same conditions. The important implications of these observations in determining the aggregation conditions promoting efficient photon upconversion by excitonic annihilation in a variety of media are thoroughly discussed.

Computation of thermodynamic and transport properties to predict thermophoretic effects in an argon-krypton mixture

NASA Astrophysics Data System (ADS)

Miller, Nicholas A. T.; Daivis, Peter J.; Snook, Ian K.; Todd, B. D.

2013-10-01

Thermophoresis is the movement of molecules caused by a temperature gradient. Here we report the results of a study of thermophoresis using non-equilibrium molecular dynamics simulations of a confined argon-krypton fluid subject to two different temperatures at thermostated walls. The resulting temperature profile between the walls is used along with the Soret coefficient to predict the concentration profile that develops across the channel. We obtain the Soret coefficient by calculating the mutual diffusion and thermal diffusion coefficients. We report an appropriate method for calculating the transport coefficients for binary systems, using the Green-Kubo integrals and radial distribution functions obtained from equilibrium molecular dynamics simulations of the bulk fluid. Our method has the unique advantage of separating the mutual diffusion and thermal diffusion coefficients, and calculating the sign and magnitude of their individual contributions to thermophoresis in binary mixtures.

Morphological instability of a thermophoretically growing deposit

NASA Technical Reports Server (NTRS)

Castillo, Jose L.; Garcia-Ybarra, Pedro L.; Rosner, Daniel E.

1992-01-01

The stability of the planar interface of a structureless solid growing from a depositing component dilute in a carrier fluid is studied when the main solute transport mechanism is thermal (Soret) diffusion. A linear stability analysis, carried out in the limit of low growth Peclet number, leads to a dispersion relation which shows that the planar front is unstable either when the thermal diffusion factor of the condensing component is positive and the latent heat release is small or when the thermal diffusion factor is negative and the solid grows over a thermally-insulating substrate. Furthermore, the influence of interfacial energy effects and constitutional supersaturation in the vicinity of the moving interface is analyzed in the limit of very small Schmidt numbers (small solute Fickian diffusion). The analysis is relevant to physical vapor deposition of very massive species on cold surfaces, as in recent experiments of organic solid film growth under microgravity conditions.

Calculation of Propulsive Nozzle Flowfields in Multidiffusing Chemically Reacting Environments. Ph.D. Thesis - Purdue Univ.

NASA Technical Reports Server (NTRS)

Kacynski, Kenneth John

1994-01-01

An advanced engineering model has been developed to aid in the analysis and design of hydrogen/oxygen chemical rocket engines. The complete multispecies, chemically reacting and multidiffusing Navier-Stokes equations are modelled, including the Soret thermal diffusion and the Dufour energy transfer terms. In addition to the spectrum of multispecies aspects developed, the model developed in this study is also conservative in axisymmetric flow for both inviscid and viscous flow environments and the boundary conditions employ a viscous, chemically reacting, reference plane characteristics method. Demonstration cases are presented for a 1030:1 area ratio nozzle, a 25 lbf film cooled nozzle, and a transpiration cooled plug and spool rocket engine. The results indicate that the thrust coefficient predictions of the 1030:1 and the 25 lbf film cooled nozzle are within 0.2 to 0.5 percent, respectively, of experimental measurements when all of the chemical reaction and diffusion terms are considered. Further, the model's predictions agree very well with the heat transfer measurements made in all of the nozzle test cases. The Soret thermal diffusion term is demonstrated to have a significant effect on the predicted mass fraction of hydrogen along the wall of the nozzle in both the laminar flow 1030:1 nozzle and the turbulent flow plug and spool nozzle analysis cases performed. Further, the Soret term was shown to represent an important fraction of the diffusion fluxes occurring in a transpiration cooled rocket engine.

Energy minimization in nematic liquid crystal systems driven by geometric confinement and temperature gradients with applications in colloidal systems

NASA Astrophysics Data System (ADS)

Kolacz, Jakub

We first explore the topology of liquid crystals and look at the fundamental limitations of liquid crystals in confined geometries. The properties of liquid crystal droplets are studied both theoretically and through simulations. We then demonstrate a method of chemically patterning surfaces that allows us to generate periodic arrays of micron-sized liquid crystal droplets and compare them to our simulation results. The parallelizable method of self-localizing liquid crystals using 2D chemical patterning developed here has applications in liquid crystal biosensors and lens arrays. We also present the first work looking at colloidal liquid crystals under the guise of thermophoresis. We observe that strong negative thermophoresis occurs in these systems and develop a theory based on elastic energy minimization. We also calculate a Soret coefficient two orders of magnitude larger than those present in the literature. This large Soret coefficient has considerable potential for improving thermophoretic sorting mechanisms such as Thermal-Field Flow Fractionation and MicroScale Thermophoresis. The final piece of this work demonstrates a method of using projection lithography to polymerize liquid crystal colloids with a defined internal director. While still a work in progress, there is potential for generating systems of active colloids that can change shape upon external stimulus and in the generation of self-folding shapes by selective polymerization and director predetermination in the vain of micro-kirigami.

Influence of convection on microstructure

NASA Technical Reports Server (NTRS)

Wilcox, William R.; Caram, Rubens; Mohanty, A. P.; Seth, Jayshree

1990-01-01

The mechanism responsible for the difference in microstructure caused by solidifying the MnBi-Bi eutectic in space is sought. The objectives for the three year period are as follows: (1) completion of the following theoretical analyses - determination of the influence of the Soret effect on the average solid composition versus distance of off-eutectic mixtures directionally solidified in the absence of convection, determination of the influence of convection on the microstructure of off-eutectic mixtures using a linear velocity profile in the adjacent melt, determination of the influence of volumetric changes during solidification on microconvection near the freezing interface and on microstructure, and determination of the influence of convection on microstructure when the MnBi fibers project out in front of the bismuth matrix; (2) search for patterns in the effect of microgravity on different eutectics (for example, eutectic composition, eutectic temperature, usual microstructure, densities of pure constituents, and density changes upon solidification); and (3) determination of the Soret coefficient and the diffusion coefficient for Mn-Bi melts near the eutectic composition, both through laboratory experiements to be performed here and from data from Shuttle experiments.

Influence of convection on microstructure

NASA Technical Reports Server (NTRS)

Wilcox, William R.; Caram, Rubens; Mohanty, A. P.; Seth, Jayshree

1990-01-01

In eutectic growth, as the solid phases grow they reject atoms to the liquid. This results in a variation of melt composition along the solid/liquid interface. In the past, mass transfer in eutectic solidification, in the absence of convection, was considered to be governed only by the diffusion induced by compositional gradients. However, mass transfer can also be generated by a temperature gradient. This is called thermotransport, thermomigration, thermal diffusion or the Soret effect. A theoretical model of the influence of the Soret effect on the growth of eutectic alloys is presented. A differential equation describing the compositional field near the interface during unidirectional solidification of a binary eutectic alloy was formulated by including the contributions of both compositional and thermal gradients in the liquid. A steady-state solution of the differential equation was obtained by applying appropriate boundary conditions and accounting for heat flow in the melt. Following that, the average interfacial composition was converted to a variation of undercooling at the interface, and consequently to microstructural parameters. The results obtained show that thermotransport can, under certain circumstances, be a parameter of paramount importance.

Influence of convection on microstructure

NASA Technical Reports Server (NTRS)

Wilcox, William R.; Regel, Liya L.

1992-01-01

The primary motivation for this research has been to determine the cause for space processing altering the microstructure of some eutectics, especially the MnBi-Bi eutectic. Prior experimental research at Grumman and here showed that the microstructure of MnBi-Bi eutectic is twice as fine when solidified in space or in a magnetic field, is uninfluenced by interfacial temperature gradient, adjusts very quickly to changes in freezing rate, and becomes coarser when spin-up/spin-down (accelerated crucible rotation technique) is used during solidification. Theoretical work at Clarkson predicted that buoyancy driven convection on earth could not account for the two fold change in fiber spacing caused by solidification in space. However, a lamellar structure with a planar interface was assumed, and the Soret effect was not included in the analysis. Experimental work at Clarkson showed that the interface is not planar, and that MnBi fibers project out in front of the Bi matrix on the order of one fiber diameter. Originally four primary hypotheses were to be tested under this current grant: (1) a fibrous microstructure is much more sensitive to convection than a lamellar microstructure, which was assumed in our prior theoretical treatment; (2) an interface with one phase projecting out into the melt is much more sensitive to convection than a planar interface, which was assumed in our prior theoretical treatment; (3) the Soret effect is much more important in the absence of convection and has a sufficiently large influence on microstructure that its action can explain the flight results; and (4) the microstructure is much more sensitive to convection when the composition of the bulk melt is off eutectic. As reported previously, we have learned that while a fibrous microstructure and a non-planar interface are more sensitive to convection than a lamellar microstructure with a planar interface, the influence of convection remains too small to explain the flight and magnetic field results. Similarly addition of the Soret effect does not explain the flight and magnetic field results.

On the effect of thermodiffusion on solute segregation during the growth of semiconductor materials by the vertical Bridgman method

NASA Astrophysics Data System (ADS)

Ben Sassi, Mokhtar; Kaddeche, Slim; Lappa, Marcello; Millet, Séverine; Henry, Daniel; Ben Hadid, Hamda

2017-01-01

The effect of thermodiffusion on dopant distribution in the melt and in the grown crystal is investigated numerically for a vertical Bridgman configuration for situations of pure thermal convection corresponding to dilute alloys. The dopant distribution is shown to be significantly affected by the Soret parameter value. The sensitivity of the system to a variety of parameters, including the Grashof number and the so-called furnace residence time, i.e. the time during which the crucible is maintained in the furnace before initiating the solidification process, is assessed by means of parametric simulations. Moreover, the results indicate that variations in the sign of the Soret parameter can lead to diametrically opposite behaviors, while an increase in the intensity of the thermal convection generally leads to a mitigation of the effects induced by thermodiffusion. On the basis of the numerical results some useful criteria are drawn which could help crystal growers to discern the complex interrelations among the various parameters under one's control (that are not independent of one another) and to elaborate rational guidelines relating to strategies to be used to improve the quality of the resulting crystals.

Cross-diffusive effects on the onset of double-diffusive convection in a horizontal saturated porous fluid layer heated and salted from above

NASA Astrophysics Data System (ADS)

Rajib, Basu; C. Layek, G.

2013-05-01

Double-diffusive stationary and oscillatory instabilities at the marginal state in a saturated porous horizontal fluid layer heated and salted from above are investigated theoretically under the Darcy's framework for a porous medium. The contributions of Soret and Dufour coefficients are taken into account in the analysis. Linear stability analysis shows that the critical value of the Darcy—Rayleigh number depends on cross-diffusive parameters at marginally stationary convection, while the marginal state characterized by oscillatory convection does not depend on the cross-diffusion terms even if the condition and frequency of oscillatory convection depends on the cross-diffusive parameters. The critical value of the Darcy—Rayleigh number increases with increasing value of the solutal Darcy—Rayleigh number in the absence of cross-diffusive parameters. The critical Darcy—Rayleigh number decreases with increasing Soret number, resulting in destabilization of the system, while its value increases with increasing Dufour number, resulting in stabilization of the system at the marginal state characterized by stationary convection. The analysis reveals that the Dufour and Soret parameters as well as the porosity parameter play an important role in deciding the type of instability at the onset. This analysis also indicates that the stationary convection is followed by the oscillatory convection for certain fluid mixtures. It is interesting to note that the roles of cross-diffusive parameters on the double-diffusive system heated and salted from above are reciprocal to the double-diffusive system heated and salted from below.

J-aggregation in porphyrin nanoparticles induced by diphenylalanine

NASA Astrophysics Data System (ADS)

Li, Fengqing; Liu, Dongzhi; Wang, Tianyang; Hu, Jianxin; Meng, Fancui; Sun, Haiya; Shang, Zhi; Li, Pingan; Feng, Wenhui; Li, Wei; Zhou, Xueqin

2017-08-01

In this report, L-diphenylalanine-decorated tetraphenylporphyrin (TPPtFFC) was synthesized and self-assembled into regular nano-architechtures. The morphology of the assemblies varied with the concentration of TPPtFFC. The absorption spectra of the nanoparticles show the Soret band merges with the Q bands and redistributes with great red-shift, indicative of the formation of J-aggregates of the porphyrin molecules. The fluorescence emission of the nanoparticles is merged and red-shifted to near-infrared region. Studies of absorption and fluorescence spectra reveal an indispensible role of diphenylalanine group in the formation of J-aggregates. The Raman spectra disclose that diprotonation of the porphyrin core contributes to delocalized coherent excited states in the nanoparticles. The positive cotton effect in circular dichroism spectra corresponding to the Soret band of TPPtFFC in solution confirms the formation of J-aggregates with right-handed chirality of the dipole moment. This report will shed light on the rational design of porphyrin-peptide conjugates to mimic naturally light-harvesting complexes.

[Effect of stress actions on some hematologic and biochemical parameters of rat blood and on energetic intermolecular interactions in lipid extract under effect of light radiation].

PubMed

Zabelinskiĭ, S A; Chebotareva, M A; Tavrovskaia, T V; Skverchinskaia, E A; Shukoliukova, E P; Maslov, M N; Krivchenko, A I

2012-01-01

Comparative study has been carried of effect of the three-day long starvation, running, and their combination on morphological parameters of rat blood, lipid metabolism, and activity of blood Na,K-ATPase. Different effect has been shown of these stress factors on the blood erythrocyte composition. Starvation is accompanied by the most pronounced release of stored erythrocyte into blood, which results in a significant decrease both of the total amount of reticulocytes and the complete absence of reticulocytes of the I stage of maturity (the youngest). The running on treadmill led to a significant increase of the total amount of blood reticulocytes and to multiple increase of immature reticulocytes (RC-I and RC-II), which can indicate some stress of the bone marrow erythroid stem line. The curve of acid resistance of blood reticulocytes has shown the animal to experience the greatest stress at a combination of starvation and running. Starvation and running produced different effects on blood lipid characteristics. The content of triacylglycerides (TAG) in blood rose by 40% at starvation and decreased by 30% at running, a similar tendency being found for index of atherogeneity. The fatty acid composition of blood phospholipids at running and its combination with starvation practically did not differ from control. A change of Na,K-ATPase, which is so characteristic of reaction to various kinds of stress, sharply fell at starvation (by 22%), but increased at running (by 13%) and decreased markedly at combination of these actions. Absorption spectra of lipid extracts of the whole blood of the rats submitted to various stress actions showed that extracted from blood (at different amount depending on the kind of action) is an organic substance with coupled bonds, which absorbs light in the diapason of 360-620 nm. The absorption of light in the diapason of 400-410 nm has been found to belong to the Soret band of ferroheme and ferriheme. The shift of the Soret band indicates electron transitions in the iron cation. By the change and disappearance of the Soret band, it is possible to judge about the processes occurring in the lipid extract. The disappearance of the Soret band in the lipid extract indicates formation in it of steady radicals as a result of the ferriheme disintegration due to accumulation of energy in porphyrin, which does not seem to occur in the blood cell membranes. The iron atom in the ferriheme molecule is known to accept electron and yields a part of energy probably to porphyrin. Then ferriheme yields electron and becomes ferriheme with excess of energy in porphyrin. Hence, at admission of the next electron to the iron atom the porphyrin molecule is to get rid of the energy obtained earlier to prevent its disintegration. The heme is possible to be an accumulator and distributor of energy in tissue.

Photophysics of self-assembled zinc porphyrin-bidentate diamine ligand complexes.

PubMed

Danger, Brook R; Bedient, Krysta; Maiti, Manisankar; Burgess, Ian J; Steer, Ronald P

2010-10-21

The effects of complexation--by bidentate nitrogen-containing ligands such as pyrazine and 4,4'-bipyridine commonly used for porphyrin self-assembly--on the photophysics of the model metalloporphyrin, ZnTPP, are reported. Ligation to form the 5-coordinate species introduces an intramolecular charge transfer (ITC) state that, depending on the oxidation and reduction potentials of the electron donor and acceptor, can become involved in the excited state relaxation processes. For ZnTPP, ligation with pyridine has little effect on excited state relaxation following either Q-band or Soret band excitation. However, coordination of ZnTPP with pyrazine and bipyridine causes the S(2) (Soret) state of the ligated species to decay almost exclusively via an S(2)-ICT-S(1) pathway, while affecting the S(1) decay route only slightly. In these 5-coordinate species the S(2)-ICT-S(1) decay route is ultrafast and nearly quantitative. Literature redox data for other bidentate ligands such as DABCO and multidentate ligands commonly used for pophyrin assembly suggest that the ITC states introduced by them could also modify the excited state relaxation dynamics of a wide variety of multiporphyrin arrays.

An improved molecular dynamics algorithm to study thermodiffusion in binary hydrocarbon mixtures

NASA Astrophysics Data System (ADS)

Antoun, Sylvie; Saghir, M. Ziad; Srinivasan, Seshasai

2018-03-01

In multicomponent liquid mixtures, the diffusion flow of chemical species can be induced by temperature gradients, which leads to a separation of the constituent components. This cross effect between temperature and concentration is known as thermodiffusion or the Ludwig-Soret effect. The performance of boundary driven non-equilibrium molecular dynamics along with the enhanced heat exchange (eHEX) algorithm was studied by assessing the thermodiffusion process in n-pentane/n-decane (nC5-nC10) binary mixtures. The eHEX algorithm consists of an extended version of the HEX algorithm with an improved energy conservation property. In addition to this, the transferable potentials for phase equilibria-united atom force field were employed in all molecular dynamics (MD) simulations to precisely model the molecular interactions in the fluid. The Soret coefficients of the n-pentane/n-decane (nC5-nC10) mixture for three different compositions (at 300.15 K and 0.1 MPa) were calculated and compared with the experimental data and other MD results available in the literature. Results of our newly employed MD algorithm showed great agreement with experimental data and a better accuracy compared to other MD procedures.

Effet d'un champ magnétique uniforme sur les instabilités de Rayleigh-Bénard avec effet Soret

NASA Astrophysics Data System (ADS)

Ben Sassi, Mokhtar; Kaddeche, Slim; Abdennadher, Ali; Henry, Daniel; Hadid, Hamda Ben; Mojtabi, Abdelkader

2016-01-01

The effect of both magnitude and orientation of a uniform magnetic field on the critical transition occurring within an electrically conducting binary fluid layer, stratified in temperature and concentration, taking into account the Soret effect, is investigated numerically. For such a configuration, the results show that the critical thresholds corresponding to an arbitrary orientated magnetic field can be derived from those obtained for a vertical magnetic field and that the axes of the marginal cells are aligned with the horizontal component of the magnetic field. Moreover, an analytical study is conducted to investigate the impact of the magnetic field on long-wavelength instabilities. The effect of the magnetic field on such instabilities reveals a new phenomenon consisting in major changes of the unstable modes that lose their unicellular nature to regain their multi-roll characteristic, as it is the case without magnetic field for ψ <ψℓ0 = 131 Le / (34 - 131 Le). For a binary fluid characterized by a Lewis number Le and a separation factor ψ >ψℓ0, the value of the Hartmann number Haℓ (ψ , Le) corresponding to that transition responsible for a significant change in mass and heat transfer can be determined from the analytical relations derived in this work.

Magnesium and iron isotopes in 2.7 Ga Alexo komatiites: Mantle signatures, no evidence for Soret diffusion, and identification of diffusive transport in zoned olivine

NASA Astrophysics Data System (ADS)

Dauphas, Nicolas; Teng, Fang-Zhen; Arndt, Nicholas T.

2010-06-01

Komatiites from Alexo, Canada, are well preserved and represent high-degree partial mantle melts (˜50%). They are thus well suited for investigating the Mg and Fe isotopic compositions of the Archean mantle and the conditions of magmatic differentiation in komatiitic lavas. High precision Mg and Fe isotopic analyses of 22 samples taken along a 15-m depth profile in a komatiite flow are reported. The δ 25Mg and δ 26Mg values of the bulk flow are -0.138 ± 0.021‰ and -0.275 ± 0.042‰, respectively. These values are indistinguishable from those measured in mantle peridotites and chondrites, and represent the best estimate of the composition of the silicate Earth from analysis of volcanic rocks. Excluding the samples affected by secondary Fe mobilization, the δ 56Fe and δ 57Fe values of the bulk flow are +0.044 ± 0.030‰, and +0.059 ± 0.044‰, respectively. These values are consistent with a near-chondritic Fe isotopic composition of the silicate Earth and minor fractionation during komatiite magma genesis. In order to explain the early crystallization of pigeonite relative to augite in slowly cooled spinifex lavas, it was suggested that magmas trapped in the crystal mush during spinifex growth differentiated by Soret effect, which should be associated with large and coupled variations in the isotopic compositions of Mg and Fe. The lack of variations in Mg and Fe isotopic ratios either rules out the Soret effect in the komatiite flow or the effect is effaced as the solidification front migrates downward through the flow crust. Olivine separated from a cumulate sample has light δ 56Fe and slightly heavy δ 26Mg values relative to the bulk flow, which modeling shows can be explained by kinetic isotope fractionation associated with Fe-Mg inter-diffusion in olivine. Such variations can be used to identify diffusive processes involved in the formation of zoned minerals.

On the Convection of a Binary Mixture in a Horizontal Layer Under High-frequency Vibrations

NASA Astrophysics Data System (ADS)

Smorodin, B. L.; Ishutov, S. M.; Myznikova, B. I.

2018-02-01

The convective instability and non-linear flows are considered in a horizontal, binary-mixture layer with negative Soret coupling, subjected to the high-frequency vibration whose axis is directed at an arbitrary angle to the layer boundaries. The limiting case of long-wave disturbances is studied using the perturbation method. The influence of the intensity and direction of vibration on the spatially-periodic traveling wave solution is analyzed. It is shown that the shift in the Rayleigh number range, in which the traveling wave regime exists, toward higher values is a response to a horizontal-to-vertical transition in the vibration axis orientation. The characteristics of amplitude- and phase-modulated traveling waves are obtained and discussed.

Photoinduced Charge Transport Spectra for Porphyrin and Naphthalene Derivative-based Dendrimers

NASA Astrophysics Data System (ADS)

Park, J. H.; Wu, Y.; Parquette, J. R.; Epstein, A. J.

2006-03-01

Dendrimers are important chemical structures for harvesting charge. We prepared model dendrimers using two porphyrin derivatives and a naphthalene derivative. Films of these porphyrin derivatives have a strong Soret band (˜430nm) and four significant Q-bands; the naphthalene derivative has strong absorption at 365 and 383nm. Two kinds of photovoltaic cell structures [ITO/BaytronP/(thick or thin) dendrimer/Al] are constructed to investigate the optical response spectra of dendrimers under electric potential(V) on the cell (range from -1V to 2V). To obtain pure optical responses, incident light is modulated with an optical chopper and a lock-in amplifier is used to measure current (IAC) and phase (θ). For the excitation of the Soret band, IAC and θ do not change substantially with change of sign and amplitude of V. For Q-bands and naphthalene absorption bands, θ nearly follows the polarity of V on the cells and IAC is linear with V. Hence, IAC is nearly ohmic for Q- band although there are shifts due to built-in-potential. IAC for Soret band is almost same for thick and thin active layer cells. In contrast, IAC increases with thickness increase for Q bands. Mechanisms of photogeneration and charge transport will be discussed.

Mass transport properties of the tetrahydronaphthalene/n-dodecane mixture measured by investigating non-equilibrium fluctuations

NASA Astrophysics Data System (ADS)

Croccolo, Fabrizio; Scheffold, Frank; Bataller, Henri

2013-04-01

We present preliminary near-field light scattering (NFS) data concerning the analysis of the static power spectrum and of the relaxation time constant as a function of the wave vector for non-equilibrium fluctuations (NEFs). The goal of these measurements is to obtain information about the Soret and the mass diffusion coefficients of a binary mixture undergoing thermodiffusion. In particular, we show how the interaction between NEFs and the gravity force gives rise to a critical wavelength that provides additional information about the Soret coefficient. We suggest that a quantitative analysis can be performed by means of this non-invasive optical technique. In our setup, the sample is monitored parallel to the imposed temperature gradient, thus being insensitive to the refractive index profile along the vertical axis, while at the same time we are able to detect the light scattered by the refractive index fluctuations in horizontal planes. We select a shadowgraph layout for the NFS setup due to the extremely small wave vectors we aim to analyze. From a double-frame differential analysis of the acquired images, we obtain both the static power spectrum and the dynamics of NEFs. As a proof-of-principle experiment, we present Soret and diffusion coefficient data on a liquid mixture of tetrahydronaphthalene/n-dodecane.

Thermodiffusion, molecular diffusion and Soret coefficient of binary and ternary mixtures of n-hexane, n-dodecane and toluene.

PubMed

Alonso de Mezquia, David; Wang, Zilin; Lapeira, Estela; Klein, Michael; Wiegand, Simone; Mounir Bou-Ali, M

2014-11-01

In this study, the thermodiffusion, molecular diffusion, and Soret coefficients of 12 binary mixtures composed of toluene, n-hexane and n-dodecane in the whole range of concentrations at atmospheric pressure and temperatures of 298.15 K and 308.15 K have been determined. The experimental measurements have been carried out using the Thermogravitational Column, the Sliding Symmetric Tubes and the Thermal Diffusion Forced Rayleigh Scattering techniques. The results obtained using the different techniques show a maximum deviation of 9% for the thermodiffusion coefficient, 8% for the molecular diffusion coefficient and 2% for the Soret coefficient. For the first time we report a decrease of the thermodiffusion coefficient with increasing ratio of the thermal expansion coefficient and viscosity for a binary mixture of an organic ring compound with a short n-alkane. This observation is discussed in terms of interactions between the different components. Additionally, the thermogravitational technique has been used to measure the thermodiffusion coefficients of four ternary mixtures consisting of toluene, n-hexane and n-dodecane at 298.15 K. In order to complete the study, the values obtained for the molecular diffusion coefficient in binary mixtures, and the thermodiffusion coefficient of binary and ternary mixtures have been compared with recently derived correlations.

Using stepped anvils to make even insulation layers in laser-heated diamond-anvil cell samples

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

Du, Zhixue; Gu, Tingting; Dobrosavljevic, Vasilije

Here, we describe a method to make even insulation layers for high-pressure laser-heated diamond-anvil cell samples using stepped anvils. Moreover, the method works for both single-sided and double-sided laser heating using solid or fluid insulation. The stepped anvils are used as matched pairs or paired with a flat culet anvil to make gasket insulation layers and not actually used at high pressures; thus, their longevity is ensured. We also compare the radial temperature gradients and Soret diffusion of iron between self-insulating samples and samples produced with stepped anvils and find that less pronounced Soret diffusion occurs in samples with evenmore » insulation layers produced by stepped anvils.« less

Using stepped anvils to make even insulation layers in laser-heated diamond-anvil cell samples

DOE PAGES

Du, Zhixue; Gu, Tingting; Dobrosavljevic, Vasilije; ...

2015-09-01

Here, we describe a method to make even insulation layers for high-pressure laser-heated diamond-anvil cell samples using stepped anvils. Moreover, the method works for both single-sided and double-sided laser heating using solid or fluid insulation. The stepped anvils are used as matched pairs or paired with a flat culet anvil to make gasket insulation layers and not actually used at high pressures; thus, their longevity is ensured. We also compare the radial temperature gradients and Soret diffusion of iron between self-insulating samples and samples produced with stepped anvils and find that less pronounced Soret diffusion occurs in samples with evenmore » insulation layers produced by stepped anvils.« less

Cross diffusion and exponential space dependent heat source impacts in radiated three-dimensional (3D) flow of Casson fluid by heated surface

NASA Astrophysics Data System (ADS)

Zaigham Zia, Q. M.; Ullah, Ikram; Waqas, M.; Alsaedi, A.; Hayat, T.

2018-03-01

This research intends to elaborate Soret-Dufour characteristics in mixed convective radiated Casson liquid flow by exponentially heated surface. Novel features of exponential space dependent heat source are introduced. Appropriate variables are implemented for conversion of partial differential frameworks into a sets of ordinary differential expressions. Homotopic scheme is employed for construction of analytic solutions. Behavior of various embedding variables on velocity, temperature and concentration distributions are plotted graphically and analyzed in detail. Besides, skin friction coefficients and heat and mass transfer rates are also computed and interpreted. The results signify the pronounced characteristics of temperature corresponding to convective and radiation variables. Concentration bears opposite response for Soret and Dufour variables.

Symbolic Computational Approach to the Marangoni Convection Problem With Soret Diffusion

NASA Technical Reports Server (NTRS)

Skarda, J. Raymond

1998-01-01

A recently reported solution for stationary stability of a thermosolutal system with Soret diffusion is re-derived and examined using a symbolic computational package. Symbolic computational languages are well suited for such an analysis and facilitate a pragmatic approach that is adaptable to similar problems. Linearization of the equations, normal mode analysis, and extraction of the final solution are performed in a Mathematica notebook format. An exact solution is obtained for stationary stability in the limit of zero gravity. A closed form expression is also obtained for the location of asymptotes in relevant parameter, (Sm(sub c), Mac(sub c)), space. The stationary stability behavior is conveniently examined within the symbolic language environment. An abbreviated version of the Mathematica notebook is given in the Appendix.

Modeling of liquid and gas flows in the horizontal layer with evaporation

NASA Astrophysics Data System (ADS)

Lyulin, Yuri; Rezanova, Ekaterina

2017-10-01

Mathematical modeling of two-layer flows in the "ethanol-nitrogen" system on the basis of the exact solutions of a special type is carried out. The influence of the gas flow, temperature and Soret effect on the flow patterns and evaporating processes at the interface is investigated. The results of comparison of the experimental and theoretical data are presented; the dependence of the evaporation intensity at interface of the gas flow rate and temperature is studied.

The prediction of nozzle performance and heat transfer in hydrogen/oxygen rocket engines with transpiration cooling, film cooling, and high area ratios

NASA Technical Reports Server (NTRS)

Kacynski, Kenneth J.; Hoffman, Joe D.

1993-01-01

An advanced engineering computational model has been developed to aid in the analysis and design of hydrogen/oxygen chemical rocket engines. The complete multi-species, chemically reacting and diffusing Navier-Stokes equations are modelled, finite difference approach that is tailored to be conservative in an axisymmetric coordinate system for both the inviscid and viscous terms. Demonstration cases are presented for a 1030:1 area ratio nozzle, a 25 lbf film cooled nozzle, and transpiration cooled plug-and-spool rocket engine. The results indicate that the thrust coefficient predictions of the 1030:1 nozzle and the film cooled nozzle are within 0.2 to 0.5 percent, respectively, of experimental measurements when all of the chemical reaction and diffusion terms are considered. Further, the model's predictions agree very well with the heat transfer measurements made in all of the nozzle test cases. The Soret thermal diffusion term is demonstrated to have a significant effect on the predicted mass fraction of hydrogen along the wall of the nozzle in both the laminar flow 1030:1 nozzle and the turbulent plug-and-spool rocket engine analysis cases performed. Further, the Soret term was shown to represent a significant fraction of the diffusion fluxes occurring in the transpiration cooled rocket engine.

Strong Impact of an Axial Ligand on the Absorption by Chlorophyll a and b Pigments Determined by Gas-Phase Ion Spectroscopy Experiments.

PubMed

Kjær, Christina; Stockett, Mark H; Pedersen, Bjarke M; Nielsen, Steen Brøndsted

2016-12-01

The microenvironments in photosynthetic proteins affect the absorption by chlorophyll (Chl) pigments. It is, however, a challenge to disentangle the impact on the transition energies of different perturbations, for example, the global electrostatics of the protein (nonbonded environmental effects), exciton coupling between Chl's, conformational variations, and binding of an axial ligand to the magnesium center. This is needed to distinguish between the two most commonly proposed mechanisms for energy transport in photosynthetic proteins, relying on either weakly or strongly coupled pigments. Here, on the basis of photodissociation action spectroscopy, we establish that the redshift of the Soret absorption band due to binding of a negatively charged carboxylate (as present in aspartic acid and glutamic acid residues) is 0.1-0.2 eV for Chl a and b. This effect is almost enough to reproduce the well-known green color of plants and can account for the strong spectral variation between Chl's. The experimental data serve to benchmark future high-level calculations of excited-state energies. Finally, we demonstrate that complexes between Chl a and histidine, tagged by a quaternary ammonium ion, can be made in the gas phase by electrospray ionization, but more work is needed to produce enough ions for gas-phase spectroscopy.

Effect of radial magnetic field on peristaltic transport of Jeffrey fluid in curved channel with heat / mass transfer

NASA Astrophysics Data System (ADS)

Abdulhadi, Ahmed M.; Ahmed, Tamara S.

2018-05-01

In this paper, we deals with the impact of radialiy magnetic field on the peristaltic transport of Jeffrey fluid through a curved channel with two dimensional. The effect of slip condition on velocity, the non-slip condition on temperature and conversation is performed. The heat and mass transfer are considered under the influence of various parameters. The flow is investigated under the assumption of long wave length and low Reynolds number approximations. The distribution of temperature and concentration are discussed for various parameters governing the flow with the simultaneous effects of Brinkman number, Soret number and Schmidt number.

Transient cage formation around hot gold colloids dispersed in polymer solutions.

PubMed

Schwaiger, F; Zimmermann, W; Köhler, W

2011-12-14

Gold colloids dispersed in dilute to concentrated polymer solutions can efficiently be heated by laser irradiation and act as almost pointlike heat sources. In systems with positive Soret coefficients S(T) of the polymer, such as solutions of polystyrene in toluene, the polymer can almost entirely be removed from the particle surface. The colloid attracts the solvent and a transient cage of low viscosity and dramatically enhanced mobility is formed, which follows the motion of the particle with a certain retardation. Based on a complete parameterization of S(T)(M, c, T), we analyze in detail the stationary temperature, concentration, and viscosity profiles. Depending on the polymer molar mass and concentration on the distance to the glass transition temperature, the negative or positive feedback-loops are established that lead to either attenuation or self-amplification of the polymer depletion. © 2011 American Institute of Physics

Kuipers works with DSC Hardware in the U.S. Laboratory

NASA Image and Video Library

2012-01-16

ISS030-E-155917 (16 Jan. 2012) --- European Space Agency astronaut Andre Kuipers, Expedition 30 flight engineer, prepares to place Diffusion Soret Coefficient (DSC) hardware in stowage containers in the Destiny laboratory of the International Space Station.

Thermophoretic torque in colloidal particles with mass asymmetry

NASA Astrophysics Data System (ADS)

Olarte-Plata, Juan; Rubi, J. Miguel; Bresme, Fernando

2018-05-01

We investigate the response of anisotropic colloids suspended in a fluid under a thermal field. Using nonequilibrium molecular dynamics computer simulations and nonequilibrium thermodynamics theory, we show that an anisotropic mass distribution inside the colloid rectifies the rotational Brownian motion and the colloids experience transient torques that orient the colloid along the direction of the thermal field. This physical effect gives rise to distinctive changes in the dependence of the Soret coefficient with colloid mass, which features a maximum, unlike the monotonic increase of the thermophoretic force with mass observed in homogeneous colloids.

Ultrafast dynamics of ligand and substrate interaction in endothelial nitric oxide synthase under Soret excitation.

PubMed

Hung, Chih-Chang; Yabushita, Atsushi; Kobayashi, Takayoshi; Chen, Pei-Feng; Liang, Keng S

2016-01-01

Ultrafast transient absorption spectroscopy of endothelial NOS oxygenase domain (eNOS-oxy) was performed to study dynamics of ligand or substrate interaction under Soret band excitation. Photo-excitation dissociates imidazole ligand in <300fs, then followed by vibrational cooling and recombination within 2ps. Such impulsive bond breaking and late rebinding generate proteinquakes, which relaxes in several tens of picoseconds. The photo excited dynamics of eNOS-oxy with L-arginine substrate mainly occurs at the local site of heme, including ultrafast internal conversion within 400fs, vibrational cooling, charge transfer, and complete ground-state recovery within 1.4ps. The eNOS-oxy without additive is partially bound with water molecule, thus its photoexcited dynamics also shows ligand dissociation in <800fs. Then it followed by vibrational cooling coupled with charge transfer in 4.8ps, and recombination of ligand to distal side of heme in 12ps. Copyright © 2016 Elsevier B.V. All rights reserved.

Investigation of focusing and correcting aberrations with binary amplitude and polarization modulation

DOE PAGES

Fiala, Peter; Li, Yunqi; Dorrer, Christophe

2018-01-29

Here, we investigate the focusing and correcting wavefront aberration of an optical wave using binary amplitude and polarization modulation. Focusing is performed by selectively modulating the field in different zones of the pupil to obtain on-axis constructive interference at a given distance. The conventional Soret zone plate (binary amplitude profile) is expanded to a polarization Soret zone plate with twice the focusing efficiency. Binary pixelated devices that approximate the sinusoidal transmission profile of a Gabor zone plate by spatial dithering are also investigated with amplitude and polarization modulation. Wavefront aberrations are corrected by modulation of the field in the pupilmore » plane to prevent destructive interference in the focal plane of an ideal focusing element. Polarization modulation improves the efficiency obtained by amplitude-only modulation, with a gain that depends on the aberration. Experimental results obtained with Cr-on-glass devices for amplitude modulation and liquid crystal devices operating in the Mauguin condition for polarization modulation are in very good agreement with simulations.« less

Investigation of focusing and correcting aberrations with binary amplitude and polarization modulation

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

Fiala, Peter; Li, Yunqi; Dorrer, Christophe

Here, we investigate the focusing and correcting wavefront aberration of an optical wave using binary amplitude and polarization modulation. Focusing is performed by selectively modulating the field in different zones of the pupil to obtain on-axis constructive interference at a given distance. The conventional Soret zone plate (binary amplitude profile) is expanded to a polarization Soret zone plate with twice the focusing efficiency. Binary pixelated devices that approximate the sinusoidal transmission profile of a Gabor zone plate by spatial dithering are also investigated with amplitude and polarization modulation. Wavefront aberrations are corrected by modulation of the field in the pupilmore » plane to prevent destructive interference in the focal plane of an ideal focusing element. Polarization modulation improves the efficiency obtained by amplitude-only modulation, with a gain that depends on the aberration. Experimental results obtained with Cr-on-glass devices for amplitude modulation and liquid crystal devices operating in the Mauguin condition for polarization modulation are in very good agreement with simulations.« less

Photoacoustic and Photothermal Effects in Particulate Suspensions

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

Diebold, Gerald, J.

A summary of the research areas investigated by the author during the grant period is given. Experiments and theory have been carried out on the photoacoustic effect arising from a number of physical and chemical processes. A number of studies of the photoacoustic effect as it occurs in transient grating experiments have been completed. The research done with the Ludwig-Soret effect on the generation of shock waves is reported. Other research, such as that carried out on interferometric and beam deflection microphones, the use of microphones in vacuum as momentum flux detectors, and chemical generation of sonoluminescence is listed. Amore » list of published research including selected publications, a complete list of journal articles, books, review articles, and reviews are given.« less

Low-density lipoprotein transport through an arterial wall under hyperthermia and hypertension conditions--An analytical solution.

PubMed

Iasiello, Marcello; Vafai, Kambiz; Andreozzi, Assunta; Bianco, Nicola

2016-01-25

An analytical solution for Low-Density Lipoprotein transport through an arterial wall under hyperthermia conditions is established in this work. A four-layer model is used to characterize the arterial wall. Transport governing equations are obtained as a combination between Staverman-Kedem-Katchalsky membrane equations and volume-averaged porous media equations. Temperature and solute transport fields are coupled by means of Ludwig-Soret effect. Results are in excellent agreement with numerical and analytical literature data under isothermal conditions, and with numerical literature data for the hyperthermia case. Effects of hypertension combined with hyperthermia, are also analyzed in this work. Copyright © 2015 Elsevier Ltd. All rights reserved.

Computational analysis of plane and parabolic flow of MHD Carreau fluid with buoyancy and exponential heat source effects

NASA Astrophysics Data System (ADS)

Krishna, P. Mohan; Sandeep, N.; Sharma, Ram Prakash

2017-05-01

This paper presents the two-dimensional magnetohydrodynamic Carreau fluid flow over a plane and parabolic regions in the form of buoyancy and exponential heat source effects. Soret and Dufour effects are used to examine the heat and mass transfer process. The system of ODE's is obtained by utilizing similarity transformations. The RK-based shooting process is employed to generate the numerical solutions. The impact of different parameters of interest on fluid flow, concentration and thermal fields is characterized graphically. Tabular results are presented to discuss the wall friction, reduced Nusselt and Sherwood numbers. It is seen that the flow, thermal and concentration boundary layers of the plane and parabolic flows of Carreau fluid are non-uniform.

Mathematics of thermal diffusion in an exponential temperature field

NASA Astrophysics Data System (ADS)

Zhang, Yaqi; Bai, Wenyu; Diebold, Gerald J.

2018-04-01

The Ludwig-Soret effect, also known as thermal diffusion, refers to the separation of gas, liquid, or solid mixtures in a temperature gradient. The motion of the components of the mixture is governed by a nonlinear, partial differential equation for the density fractions. Here solutions to the nonlinear differential equation for a binary mixture are discussed for an externally imposed, exponential temperature field. The equation of motion for the separation without the effects of mass diffusion is reduced to a Hamiltonian pair from which spatial distributions of the components of the mixture are found. Analytical calculations with boundary effects included show shock formation. The results of numerical calculations of the equation of motion that include both thermal and mass diffusion are given.

Unravelling the hydrophobicity of urea in water using thermodiffusion: implications for protein denaturation.

PubMed

Niether, Doreen; Di Lecce, Silvia; Bresme, Fernando; Wiegand, Simone

2018-01-03

Urea is widely used as a protein denaturant in aqueous solutions. Experimental and computer simulation studies have shown that it dissolves in water almost ideally at high concentrations, introducing little disruption in the water hydrogen bonded structure. However, at concentrations of the order of 5 M or higher, urea induces denaturation in a wide range of proteins. The origin of this behaviour is not completely understood, but it is believed to stem from a balance between urea-protein and urea-water interactions, with urea becoming possibly hydrophobic at a specific concentration range. The small changes observed in the water structure make it difficult to connect the denaturation effects to the solvation properties. Here we show that the exquisite sensitivity of thermodiffusion to solute-water interactions allows the identification of the onset of hydrophobicity of urea-water mixtures. The hydrophobic behaviour is reflected in a sign reversal of the temperature dependent slope of the Soret coefficient, which is observed, both in experiments and non-equilibrium computer simulations at ∼5 M concentration of urea in water. This concentration regime corresponds to the one where abrupt changes in the denaturation of proteins are commonly observed. We show that the onset of hydrophobicity is intrinsically connected to the urea-water interactions. Our results allow us to identify correlations between the Soret coefficient and the partition coefficient, log P, hence establishing the thermodiffusion technique as a powerful approach to study hydrophobicity.

Ferric iron in primitive asteroids - A 0.43-micron absorption feature

NASA Technical Reports Server (NTRS)

Vilas, Faith; Hatch, Erin C.; Larson, Stephen M.; Sawyer, Scott R.; Gaffey, Michael J.

1993-01-01

A search of reflectance spectra of C- P-, D- and S-class asteroids to hunt for the Soret band near 0.4 micron that is indicative of porphyrins yielded an identification of an 0.43 micron absorption feature in 11 primitive asteroids of the C, P, and G classes and in one S-class asteroid. It is proposed that the feature is an Fe(3+) spin-forbidden transition in aqueously altered material, possibly located near 0.43 micron due to an enhancement effect similar to the mechanism operating in jarosite. The significance of the feature for the aqueous alteration history of these asteroids is addressed.

Cross diffusion effect on MHD mixed convection flow of nonlinear radiative heat and mass transfer of Casson fluid over a vertical plate

NASA Astrophysics Data System (ADS)

Ganesh Kumar, K.; Archana, M.; Gireesha, B. J.; Krishanamurthy, M. R.; Rudraswamy, N. G.

2018-03-01

A study on magnetohydrodynamic mixed convection flow of Casson fluid over a vertical plate has been modelled in the presence of Cross diffusion effect and nonlinear thermal radiation. The governing partial differential equations are remodelled into ordinary differential equations by using similarity transformation. The accompanied differential equations are resolved numerically by using Runge-Kutta-Fehlberg forth-fifth order along with shooting method (RKF45 Method). The results of various physical parameters on velocity and temperature profiles are given diagrammatically. The numerical values of the local skin friction coefficient, local Nusselt number and local Sherwood number also are shown in a tabular form. It is found that, effect of Dufour and Soret parameter increases the temperature and concentration component correspondingly.

Thermal diffusion effect on MHD mixed convective flow along a vertically inclined plate: A casson fluid flow

NASA Astrophysics Data System (ADS)

Prasad, D. V. V. Krishna; Chaitanya, G. S. Krishna; Raju, R. Srinivasa

2018-05-01

The nature of Casson fluid on MHD free convective flow of over an impulsively started infinite vertically inclined plate in presence of thermal diffusion (Soret), thermal radiation, heat and mass transfer effects is studied. The basic governing nonlinear coupled partial differential equations are solved numerically using finite element method. The relevant physical parameters appearing in velocity, temperature and concentration profiles are analyzed and discussed through graphs. Finally, the results for velocity profiles and the reduced Nusselt and Sherwood numbers are obtained and compared with previous results in the literature and are found to be in excellent agreement. Applications of the present study would be useful in magnetic material processing and chemical engineering systems.

Diffuse charge dynamics in ionic thermoelectrochemical systems.

PubMed

Stout, Robert F; Khair, Aditya S

2017-08-01

Thermoelectrics are increasingly being studied as promising electrical generators in the ongoing search for alternative energy sources. In particular, recent experimental work has examined thermoelectric materials containing ionic charge carriers; however, the majority of mathematical modeling has been focused on their steady-state behavior. Here, we determine the time scales over which the diffuse charge dynamics in ionic thermoelectrochemical systems occur by analyzing the simplest model thermoelectric cell: a binary electrolyte between two parallel, blocking electrodes. We consider the application of a temperature gradient across the device while the electrodes remain electrically isolated from each other. This results in a net voltage, called the thermovoltage, via the Seebeck effect. At the same time, the Soret effect results in migration of the ions toward the cold electrode. The charge dynamics are described mathematically by the Poisson-Nernst-Planck equations for dilute solutions, in which the ion flux is driven by electromigration, Brownian diffusion, and thermal diffusion under a temperature gradient. The temperature evolves according to the heat equation. This nonlinear set of equations is linearized in the (experimentally relevant) limit of a "weak" temperature gradient. From this, we show that the time scale on which the thermovoltage develops is the Debye time, 1/Dκ^{2}, where D is the Brownian diffusion coefficient of both ion species, and κ^{-1} is the Debye length. However, the concentration gradient due to the Soret effect develops on the bulk diffusion time, L^{2}/D, where L is the distance between the electrodes. For thin diffuse layers, which is the condition under which most real devices operate, the Debye time is orders of magnitude less than the diffusion time. Therefore, rather surprisingly, the majority of ion motion occurs after the steady thermovoltage has developed. Moreover, the dynamics are independent of the thermal diffusion coefficients, which simply set the magnitude of the steady-state thermovoltage.

Diffuse charge dynamics in ionic thermoelectrochemical systems

NASA Astrophysics Data System (ADS)

Stout, Robert F.; Khair, Aditya S.

2017-08-01

Thermoelectrics are increasingly being studied as promising electrical generators in the ongoing search for alternative energy sources. In particular, recent experimental work has examined thermoelectric materials containing ionic charge carriers; however, the majority of mathematical modeling has been focused on their steady-state behavior. Here, we determine the time scales over which the diffuse charge dynamics in ionic thermoelectrochemical systems occur by analyzing the simplest model thermoelectric cell: a binary electrolyte between two parallel, blocking electrodes. We consider the application of a temperature gradient across the device while the electrodes remain electrically isolated from each other. This results in a net voltage, called the thermovoltage, via the Seebeck effect. At the same time, the Soret effect results in migration of the ions toward the cold electrode. The charge dynamics are described mathematically by the Poisson-Nernst-Planck equations for dilute solutions, in which the ion flux is driven by electromigration, Brownian diffusion, and thermal diffusion under a temperature gradient. The temperature evolves according to the heat equation. This nonlinear set of equations is linearized in the (experimentally relevant) limit of a "weak" temperature gradient. From this, we show that the time scale on which the thermovoltage develops is the Debye time, 1 /D κ2 , where D is the Brownian diffusion coefficient of both ion species, and κ-1 is the Debye length. However, the concentration gradient due to the Soret effect develops on the bulk diffusion time, L2/D , where L is the distance between the electrodes. For thin diffuse layers, which is the condition under which most real devices operate, the Debye time is orders of magnitude less than the diffusion time. Therefore, rather surprisingly, the majority of ion motion occurs after the steady thermovoltage has developed. Moreover, the dynamics are independent of the thermal diffusion coefficients, which simply set the magnitude of the steady-state thermovoltage.

Voltammetric studies of hemoglobin-coated polystyrene latex bead films on pyrolytic graphite electrodes.

PubMed

Sun, Hong; Hu, Naifei

2004-08-01

A novel hemoglobin (Hb)-coated polystyrene (PS) latex bead film was deposited on pyrolytic graphite (PG) electrode surface. In the first step, positively charged Hb molecules in pH 5.0 buffers were adsorbed on the surface of negatively charged, 500 nm diameter PS latex beads bearing sulfate groups by electrostatic interaction. The aqueous dispersion of Hb-coated PS particles was then deposited on the surface of PG electrodes and, after evaporation of the solvent, Hb-PS films were formed. The Hb-PS film electrodes exhibited a pair of well-defined, quasi-reversible cyclic voltammetric (CV) peaks at about -0.36 V vs. SCE in pH 7.0 buffers, characteristic of Hb heme Fe(III)/Fe(II) redox couples. Positions of Soret absorption band of Hb-PS films suggest that Hb retains its near-native structure in the films in its dry form and in solution at medium pH. The Hb in PS films was also acted as a catalyst to catalyze electrochemical reduction of various substrates such as trichloroacetic acid (TCA), nitrite, oxygen and hydrogen peroxide.

Thermally developed peristaltic propulsion of magnetic solid particles in biorheological fluids

NASA Astrophysics Data System (ADS)

Bhatti, M. M.; Zeeshan, A.; Tripathi, D.; Ellahi, R.

2018-04-01

In this article, effects of heat and mass transfer on MHD peristaltic motion of solid particles in a dusty fluid are investigated. The effects of nonlinear thermal radiation and Hall current are also taken into account. The relevant flow analysis is modelled for fluid phase and dust phase in wave frame by means of Casson fluid model. Computation of solutions is presented for velocity profile, temperature profile and concentration profile. The effects of all the physical parameters such as particle volume fraction, Hartmann number, Hall Effect, Prandtl number, Eckert number, Schmidt number and Soret number are discussed mathematically and graphically. It is noted that the influence of magnetic field and particle volume fraction opposes the flow. Also, the impact of particle volume fraction is quite opposite on temperature and concentration profile. This model is applicable in smart drug delivery systems and bacteria movement in urine flow through the ureter.

Phosphorescence dynamics of singlet oxygen and Radachlorin photosensitizer in aqueous solution

NASA Astrophysics Data System (ADS)

Belik, V. P.; Beltukova, D. M.; Gadzhiev, I. M.; Semenova, I. V.; Vasyutinskii, O. S.

2017-07-01

The luminescence spectrum of aqueous solution of Radachlorin photosensitizer in the near IR spectral range (950-1350 nm) has been determined at the excitation in both the Soret and Q absorption bands. Major sources of the recorded luminescence were analyzed. Kinetics of photosensitizer and singlet oxygen phosphorescence signals were studied by means of time-resolved spectroscopy. The corresponding characteristic lifetimes were determined.

The reaction of fully reduced cytochrome c oxidase with oxygen studied by flow-flash spectrophotometry at room temperature. Evidence for new pathways of electron transfer.

PubMed Central

Hill, B C; Greenwood, C

1984-01-01

Absorption changes during the O2 reaction of reduced bovine cytochrome c oxidase were investigated by the rapid-reaction technique of flow-flash spectrophotometry in the Soret, visible and near-i.r. spectral regions. New features in the time courses of absorption change were observed relative to the earlier findings reported by Greenwood & Gibson [(1967) J. Biol. Chem. 242, 1782-1787]. These new features arise in the Soret and near-i.r. regions and allow the reaction to be described at all wavelengths as a composite of three exponential processes. There is a rapid O2-sensitive phase detectable in the Soret and visible region. The second phase has a rate that is somewhat less dependent on O2 concentration than is the fastest phase rate and is detectable in all three spectral regions. The rate of the third phase is almost independent of the O2 concentration and is also detectable in all spectral regions. Analysis of the three phases gives their rates and absorption amplitudes. The fast phase reaches a rate of 2.5 X 10(4) s-1 at the highest O2 concentration available at 20 degrees C, whereas the phase of intermediate rate is limited at a value of 7 X 10(3) s-1 and the slow phase rate is limited at 700 s-1. The ratios of the kinetic difference spectra for the fast phase and the slow phase do not correspond to the spectra of the individual haem centres. A branched mechanism is advanced that is able to reconcile the kinetic and static difference spectra. This mechanism suggests that some of the cytochrome a is oxidized along with cytochrome a3 in the initial O2-sensitive phase. In addition, the model requires that CuA is oxidized heterogeneously. This fits with the complex time course of oxidation observed at 830 nm while retaining CuA as virtually the sole contributor to absorbance at this wavelength. PMID:6326750

[Interaction of protein with charged colloidal particles].

PubMed

Durdenko, E V; Kuznetsova, S M; Basova, L V; Tikhonenko, S A; Saburova, E A

2011-01-01

The functional state of three proteins of different molecular weight (urease, lactate dehydrogenase, and hemoglobin) in the presence of the linear polyelectrolytes poly(allylamine hydrochloride) (PAA) and sodium poly(styrenesulfonate) (PSS) in the dissolved state and of the same polyelectrolytes bound to the surface of microspheres has been investigated. Microspheres were prepared by consecutive absorption of oppositely charged polyelectrolytes so that the outer layer of the shell was PAA for the acidic protein urease, and PSS for the alkaline proteins LDH and hemoglobin. It was shown that the dissolved polyelectrolyte completely inactivates all three proteins within one minute with a slight difference in the time constant. (By Hb inactivation are conventionally meant changes in the heme environment observed from the spectrum in the Soret band.) In the presence of microspheres, the proteins were adsorbed on their surface; in this case, more than 95% of the activity was retained within two hours. The proportion of the protein adsorbed on microspheres accounted for about 98% for urease, 72% for Hb, and 35% for LDH, as determined from the tryptophan fluorescence data. The interaction of hemoglobin with another type of charged colloidal particles, phospholipid vesicles, leads to the destruction of the tertiary structure of the protein, which made itself evident in the optical absorption spectra in the Soret band, as well as the spectra of tryptophan fluorescence and circular dichroism. In this case, according to circular dichroism, the percentage of alpha-helical structure of Hb was maintained. The differences in the physical and chemical mechanisms of interaction of proteins with these two types of charged colloidal particles that leads to differences in the degree of denaturing effects are discussed.

Nonsteroidal anti-inflammatory drugs inhibit gastric peroxidase activity.

PubMed

Banerjee, R K

1990-06-20

The peroxidase activity of the mitochondrial fraction of rat gastric mucosa was inhibited with various nonsteroidal anti-inflammatory drugs (NSAIDs) in vitro. Indomethacin was found to be more effective than phenylbutazone (PB) or acetylsalicylic acid (ASA). Mouse gastric peroxidase was also very sensitive to indomethacin inhibition. Indomethacin has no significant effect on submaxillary gland peroxidase activity of either of the species studied. Purified rat gastric peroxidase activity was inhibited 75% with 0.15 mM indomethacin showing half-maximal inhibition at 0.04 mM. The inhibition could be withdrawn by increasing the concentration of iodide but not by H2O2. NSAIDs inhibit gastric peroxidase activity more effectively at acid pH (pH 5.2) than at neutral pH. Spectral studies showed a bathochromic shift of the Soret band of the enzyme with indomethacin indicating its interaction at or near the heme part of the enzyme.

Hydrazine and hydroxylamine as probes for O2-reduction site of mitochondrial cytochrome c oxidase.

PubMed Central

Kubota, T; Yoshikawa, S

1993-01-01

Reactions of hydrazine and hydroxylamine with bovine heart cytochrome c oxidase in the fully reduced state were investigated under anaerobic conditions following the visible-Soret spectral change. Hydrazine gave a sharp band at 575 nm with 20% decrease in the alpha band at 603 nm, and hydroxylamine induced a 2 nm blue-shift for the alpha band without any clear splitting. The Soret band at 443 nm was decreased significantly in intensity, with the concomitant appearance of a shoulder with hydrazine or a peak with hydroxylamine, both near 430 nm. The dependence on pH of the affinity of these reagents for the enzyme indicates that only the deprotonated forms of these reagents bind to the enzyme, suggesting a highly hydrophobic environment of the haem ligand-biding site. These spectral changes were largely removed by addition of cyanide or CO. However, detailed analysis of these spectral changes indicates that hydrazine perturbs the shape of the spectral change induced by cyanide and hydroxylamine perturbs that induced by CO. These results suggest that these aldehyde reagents bind to haem a3 iron as well as to a second site which is most likely to be the formyl group on the haem periphery, and that these two sites bind these reagents anti-cooperatively with each other. PMID:8389138

A Blue Spectral Shift of the Hemoglobin Soret Band Correlates with the Age (Time Since Deposition) of Dried Bloodstains

PubMed Central

Hanson, Erin K.; Ballantyne, Jack

2010-01-01

The ability to determine the time since deposition of a bloodstain found at a crime scene could prove invaluable to law enforcement investigators, defining the time frame in which the individual depositing the evidence was present. Although various methods of accomplishing this have been proposed, none has gained widespread use due to poor time resolution and weak age correlation. We have developed a method for the estimation of the time since deposition (TSD) of dried bloodstains using UV-VIS spectrophotometric analysis of hemoglobin (Hb) that is based upon its characteristic oxidation chemistry. A detailed study of the Hb Soret band (λmax = 412 nm) in aged bloodstains revealed a blue shift (shift to shorter wavelength) as the age of the stain increases. The extent of this shift permits, for the first time, a distinction to be made between bloodstains that were deposited minutes, hours, days and weeks prior to recovery and analysis. The extent of the blue shift was found to be a function of ambient relative humidity and temperature. The method is extremely sensitive, requiring as little as a 1 µl dried bloodstain for analysis. We demonstrate that it might be possible to perform TSD measurements at the crime scene using a portable low-sample-volume spectrophotometer. PMID:20877468

Theoretical model for optical properties of porphyrin

NASA Astrophysics Data System (ADS)

Phan, Anh D.; Nga, Do T.; Phan, The-Long; Thanh, Le T. M.; Anh, Chu T.; Bernad, Sophie; Viet, N. A.

2014-12-01

We propose a simple model to interpret the optical absorption spectra of porphyrin in different solvents. Our model successfully explains the decrease in the intensity of optical absorption at maxima of increased wavelengths. We also prove the dependence of the intensity and peak positions in the absorption spectra on the environment. The nature of the Soret band is supposed to derive from π plasmon. Our theoretical calculations are consistent with previous experimental studies.

Shadowgraph Study of Gradient Driven Fluctuations

NASA Technical Reports Server (NTRS)

Cannell, David; Nikolaenko, Gennady; Giglio, Marzio; Vailati, Alberto; Croccolo, Fabrizio; Meyer, William

2002-01-01

A fluid or fluid mixture, subjected to a vertical temperature and/or concentration gradient in a gravitational field, exhibits greatly enhanced light scattering at small angles. This effect is caused by coupling between the vertical velocity fluctuations due to thermal energy and the vertically varying refractive index. Physically, small upward or downward moving regions will be displaced into fluid having a refractive index different from that of the moving region, thus giving rise to the enhanced scattering. The scattered intensity is predicted to vary with scattering wave vector q, as q(sup -4), for sufficiently large q, but the divergence is quenched by gravity at small q. In the absence of gravity, the long wavelength fluctuations responsible for the enhanced scattering are predicted to grow until limited by the sample dimensions. It is thus of interest to measure the mean-squared amplitude of such fluctuations in the microgravity environment for comparison with existing theory and ground based measurements. The relevant wave vectors are extremely small, making traditional low-angle light scattering difficult or impossible because of stray elastically scattered light generated by optical surfaces. An alternative technique is offered by the shadowgraph method, which is normally used to visualize fluid flows, but which can also serve as a quantitative tool to measure fluctuations. A somewhat novel shadowgraph apparatus and the necessary data analysis methods will be described. The apparatus uses a spatially coherent, but temporally incoherent, light source consisting of a super-luminescent diode coupled to a single-mode optical fiber in order to achieve extremely high spatial resolution, while avoiding effects caused by interference of light reflected from the various optical surfaces that are present when using laser sources. Results obtained for a critical mixture of aniline and cyclohexane subjected to a vertical temperature gradient will be presented. The sample was confined between two horizontal parallel sapphire plates with a vertical spacing of 1 mm. The temperatures of the sapphire plates were controlled by independent circulating water loops that used Peltier devices to add or remove heat from the room air as required. For a mixture with a temperature gradient, two effects are involved in generating the vertical refractive index gradient, namely thermal expansion and the Soret effect, which generates a concentration gradient in response to the applied temperature gradient. For the aniline/cyclohexane system, the denser component (aniline) migrates toward the colder surface. Consequently, when heating from above, both effects result in the sample density decreasing with altitude and are stabilizing in the sense that no convective motion occurs regardless of the magnitude of the applied temperature gradient. The Soret effect is strong near a binary liquid critical point, and thus the dominant effect is due to the induced concentration gradient. The results clearly show the divergence at low q and the predicted gravitational quenching. Results obtained for different applied temperature gradients at varying temperature differences from the critical temperature, clearly demonstrate the predicted divergence of the thermal diffusion ratio. Thus, the more closely the critical point is approached, the smaller becomes the temperature gradient required to generate the same signal. Two different methods have been used to generate pure concentration gradients. In the first, a sample cell was filled with a single fluid, ethylene glycol, and a denser miscible fluid, water, was added from below thus establishing a sharp interface to begin the experiment. As time went on the two fluids diffused into each other, and large amplitude fluctuations were clearly observed at low q. The effects of gravitational quenching were also evident. In the second method, the aniline/cyclohexane sample was used, and after applying a vertical temperature gradient for several hours, the top and bottom temperatures were set equal and the thermal gradient died on a time scale of seconds, leaving the Soret induced concentration gradient in place. Again, large-scale fluctuations were observed and died away slowly in amplitude as diffusion destroyed the initial concentration gradient.

Organization versus frustration: low temperature transitions in a gelatine-based gel

NASA Astrophysics Data System (ADS)

Philipp, M.; Müller, U.; Sanctuary, R.; Baller, J.; Krüger, J. K.

2008-09-01

A commercial physical gel composed of gelatine, water and glycerol shows a sol-gel transition which has been resolved by optical rotation measurements by step-wise heating the gel. This transition is not observable in the longitudinal acoustic mode measured at hypersonic frequencies with Brillouin spectroscopy. Depending on the thermal treatment of the investigated material during the sol-gel transition and within the gel state, Brillouin spectroscopy reflects tremendously different hypersonic dynamics. These distinct dynamics are responsible for the formation of different glassy states at low temperatures including that of a glass-ceramic. The large variety of super-cooled and glassy states is attributed to distinct distributions of the gel's constituents within the samples. Surprisingly, the same gel state can be produced either by annealing the gel over months or by the non-equilibrium effect of thermo-diffusion (Soret effect) in the course of some minutes.

Convective fluid flows in a horizontal channel with evaporation: analytical and experimental investigations

NASA Astrophysics Data System (ADS)

Lyulin, Y. V.; Rezanova, E. V.

2017-11-01

Heat- and mass transfer processes in a two-layer system of the liquid and gas are studied with respect to evaporation at interface. The stationary convective flows of two immiscible viscous incompressible fluids filling an infinite channel and being under action of the transverse gravitation field are studied analytically. Mathematical modeling of the flows is carried out with the help of the Navier-Stokes equations in Boussinesq approximation. The Dufour and Soret effects are taken into consideration in the gas-vapor phase. In the two-dimensional case the exact solutions of special type are constructed under condition of a given specific gas flow rate. Comparison of the analytical results with results of the physical experiments with the “liquid-gas” system like “ethanol-air” are presented.

Significance of vapor phase chemical reactions on CVD rates predicted by chemically frozen and local thermochemical equilibrium boundary layer theories

NASA Technical Reports Server (NTRS)

Gokoglu, Suleyman A.

1988-01-01

This paper investigates the role played by vapor-phase chemical reactions on CVD rates by comparing the results of two extreme theories developed to predict CVD mass transport rates in the absence of interfacial kinetic barrier: one based on chemically frozen boundary layer and the other based on local thermochemical equilibrium. Both theories consider laminar convective-diffusion boundary layers at high Reynolds numbers and include thermal (Soret) diffusion and variable property effects. As an example, Na2SO4 deposition was studied. It was found that gas phase reactions have no important role on Na2SO4 deposition rates and on the predictions of the theories. The implications of the predictions of the two theories to other CVD systems are discussed.

Numerical Analysis of an Impinging Jet Reactor for the CVD and Gas-Phase Nucleation of Titania

NASA Technical Reports Server (NTRS)

Gokoglu, Suleyman A.; Stewart, Gregory D.; Collins, Joshua; Rosner, Daniel E.

1994-01-01

We model a cold-wall atmospheric pressure impinging jet reactor to study the CVD and gas-phase nucleation of TiO2 from a titanium tetra-iso-propoxide (TTIP)/oxygen dilute source gas mixture in nitrogen. The mathematical model uses the computational code FIDAP and complements our recent asymptotic theory for high activation energy gas-phase reactions in thin chemically reacting sublayers. The numerical predictions highlight deviations from ideality in various regions inside the experimental reactor. Model predictions of deposition rates and the onset of gas-phase nucleation compare favorably with experiments. Although variable property effects on deposition rates are not significant (approximately 11 percent at 1000 K), the reduction rates due to Soret transport is substantial (approximately 75 percent at 1000 K).

Two-Photon Porphyrin Core Dendrimers for Optical Power Limiting

DTIC Science & Technology

2006-09-30

macrocycle as compared to centro- symmetric porphyrins. Lowering of the symmetry relaxes the parity selection rules for 2PA, thus making the Soret band...collection of information is estimated to average 1 hour per response, including the time for reviewing instr* - - a 9 www, yen. .c. my anu maintaining...and polymers [2]. 3. We have completed a detailed study of 2PA in symmetrical and asymmetrical (push-pull) phthalocyanines [3,4,5]. 4. We have

(Energetics of silicate melts from thermal diffusion studies)

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

Not Available

1989-01-01

Research during the past year has been concentrated in four major areas. We are continuing work initiated during the first two years on modelling thermal diffusion on multicomponent silicate liquids. We have derived appropriate relations for ternary and quaternary systems and reanalyzed experimental thermal diffusion data for the ternary system fayalite-leucite-silica. In our manuscript entitled Thermal Diffusion in Petrology'', to be published in Adv. in Phy. Geochem., we show that these model results independently recover the compositional extent and temperature of liquid immiscibility in this system. Such retrieval provides a rigorous test of our theoretical predictions and simplified treatment ofmore » complex silicate liquids reported in Geochimica Cosmochimica Acta in 1986. The usefulness of our Soret research in providing mixing energies of silicate liquids has been recently confirmed by Ghiorso (1987, Cont. Min. Pet.). This demonstration provides a strategy for incorporating Soret data into the calibration of phase equilibrium-based solution models such as the one developed by Ghiorso. During the past year we also have resumed our studies of thermal diffusion in borosilicate glasses which also exhibit liquid immiscibility. Our objectives in studying these systems are (1) to further test of our multicomponent thermal diffusion model and (2) to provide quantitative constraints on the mixing properties of these glass-forming systems which are important for evaluating their suitability for storage of high-level nuclear waste. 16 refs.« less

Cytochrome components of nitrate- and sulfate-respiring Desulfovibrio desulfuricans ATCC 27774.

PubMed Central

Liu, M C; Costa, C; Coutinho, I B; Moura, J J; Moura, I; Xavier, A V; LeGall, J

1988-01-01

Three multiheme c-type cytochromes--the tetraheme cytochrome c3 (molecular weight [MW] 13,500), a dodecaheme cytochrome c (MW 40,800), and a "split-Soret" cytochrome c (MW 51,540), which is a dimer with 2 hemes per subunit (MW 26,300)--were isolated from the soluble fraction of Desulfovibrio desulfuricans (ATCC 27774) grown under nitrate- or sulfate-respiring conditions. Two of them, the dodecaheme and the split-Soret cytochromes, showed no similarities to any of the c-type cytochromes isolated from other sulfate-reducing bacteria, while the tetraheme cytochrome c3 appeared to be analogous to the cytochrome c3 found in other sulfate-reducing bacteria. For all three multiheme c-type cytochromes isolated, the homologous proteins from nitrate- and sulfate-grown cells were indistinguishable in amino acid composition, physical properties, and spectroscopic characteristics. It therefore appears that the same c-type cytochrome components are present when D. desulfuricans ATCC 27774 cells are grown under either condition. This is in contrast to the considerable difference found in Pseudomonas perfectomarina (Liu et al., J. Bacteriol. 154:278-286, 1983), a marine denitrifier, when the cells are grown on nitrate or oxygen as the terminal electron acceptor. In addition, two spectroscopy methods capable of revealing minute structural variations in proteins provided identical information about the tetraheme cytochrome c3 from nitrate-grown and sulfate-grown cells. PMID:2848008

Low-gravity fluid dynamics and transport phenomena. Progress in Astronautics and Aeronautics. Vol. 130

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

Koster, J.N.; Sani, R.L.

1990-01-01

Various papers on low-gravity fluid dynamics and transport phenomena are presented. Individual topics addressed include: fluid management in low gravity, nucleate pool boiling in variable gravity, application of energy-stability theory to problems in crystal growth, thermosolutal convection in liquid HgCdTe near the liquidus temperature, capillary surfaces in microgravity, thermohydrodynamic instabilities and capillary flows, interfacial oscillators, effects of gravity jitter on typical fluid science experiments and on natural convection in a vertical cylinder. Also discussed are: double-diffusive convection and its effects under reduced gravity, segregation and convection in dendritic alloys, fluid flow and microstructure development, analysis of convective situations with themore » Soret effect, complex natural convection in low Prandtl number metals, separation physics, phase partitioning in reduced gravity, separation of binary alloys with miscibility gap in the melt, Ostwald ripening in liquids, particle cloud combustion in reduced gravity, opposed-flow flame spread with implications for combustion at microgravity.« less

Electronic Structure of Manganese Corroles Revisited: X-ray Structures, Optical and X-ray Absorption Spectroscopies, and Electrochemistry as Probes of Ligand Noninnocence

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

Ganguly, Sumit; MCormick, Laura J.; Conradie, Jeanet

Presented herein is a detailed multitechnique investigation of ligand noninnocence in S = 3/2 manganese corrole derivatives at the formal Mn IV oxidation state. The Soret maxima of Mn[T pXPC]Cl (T pXPC = meso-tris( p-X-phenyl)corrole, where X = CF 3, H, Me, and OMe) were found to red-shift over a range of 37 nm with increasing electron-donating character of X. For Mn[T pXPC]Ph, in contrast, the complex Soret envelopes were found to be largely independent of X. These observations suggested a noninnocent corrole •2–-like ligand for the MnCl complexes and an innocent corrole 3– ligand for the MnPh complexes. Single-crystalmore » X-ray structures of three Mn[T pXPC]Cl complexes revealed skeletal bond-length alternations indicative of a noninnocent corrole, while no such alternation was observed for Mn[T pOMePC]Ph. B3LYP density functional theory (DFT) calculations on Mn[TPC]Cl yielded strong spatial separation of the α and β spin densities, consistent with an antiferromagnetically coupled Mn III-corrole •2– description. By comparison, relatively little spatial separation of the α and β spin densities was found for Mn[TPC]Ph, consistent with an essentially Mn IV-corrole 3– description. X-ray absorption of near-edge spectroscopy (XANES) revealed a moderate blue shift of 0.6 eV for the Mn K-pre-edge of Mn[T pCF 3PC]Ph and a striking enhancement of the pre-edge intensity, relative to Mn[T pCF 3PC]Cl, consistent with a more oxidized, i.e., Mn IV, center in Mn[T pCF 3PC]Ph. Time-dependent DFT calculations indicated that the enhanced intensity of the Mn K-pre-edge of Mn[T pCF 3PC]Ph results from the extra 3d z2 hole, which mixes strongly with the Mn 4p z orbital. Combined with similar results on Fe[TPC]Cl and Fe[TPC]Ph, the present study underscores the considerable potential of metal K-edge XANES in probing ligand noninnocence in first-row transition-metal corroles. As a result, cyclic voltammetry measurements revealed highly negative first reduction potentials for the Mn[T pXPC]Ph series (~–0.95 V) as well as large electrochemical HOMO-LUMO gaps of ~1.7 V. The first reductions, however, are irreversible, suggesting cleavage of the Mn–Ph bond.« less

Electronic Structure of Manganese Corroles Revisited: X-ray Structures, Optical and X-ray Absorption Spectroscopies, and Electrochemistry as Probes of Ligand Noninnocence

DOE PAGES

Ganguly, Sumit; MCormick, Laura J.; Conradie, Jeanet; ...

2018-06-06

Presented herein is a detailed multitechnique investigation of ligand noninnocence in S = 3/2 manganese corrole derivatives at the formal Mn IV oxidation state. The Soret maxima of Mn[T pXPC]Cl (T pXPC = meso-tris( p-X-phenyl)corrole, where X = CF 3, H, Me, and OMe) were found to red-shift over a range of 37 nm with increasing electron-donating character of X. For Mn[T pXPC]Ph, in contrast, the complex Soret envelopes were found to be largely independent of X. These observations suggested a noninnocent corrole •2–-like ligand for the MnCl complexes and an innocent corrole 3– ligand for the MnPh complexes. Single-crystalmore » X-ray structures of three Mn[T pXPC]Cl complexes revealed skeletal bond-length alternations indicative of a noninnocent corrole, while no such alternation was observed for Mn[T pOMePC]Ph. B3LYP density functional theory (DFT) calculations on Mn[TPC]Cl yielded strong spatial separation of the α and β spin densities, consistent with an antiferromagnetically coupled Mn III-corrole •2– description. By comparison, relatively little spatial separation of the α and β spin densities was found for Mn[TPC]Ph, consistent with an essentially Mn IV-corrole 3– description. X-ray absorption of near-edge spectroscopy (XANES) revealed a moderate blue shift of 0.6 eV for the Mn K-pre-edge of Mn[T pCF 3PC]Ph and a striking enhancement of the pre-edge intensity, relative to Mn[T pCF 3PC]Cl, consistent with a more oxidized, i.e., Mn IV, center in Mn[T pCF 3PC]Ph. Time-dependent DFT calculations indicated that the enhanced intensity of the Mn K-pre-edge of Mn[T pCF 3PC]Ph results from the extra 3d z2 hole, which mixes strongly with the Mn 4p z orbital. Combined with similar results on Fe[TPC]Cl and Fe[TPC]Ph, the present study underscores the considerable potential of metal K-edge XANES in probing ligand noninnocence in first-row transition-metal corroles. As a result, cyclic voltammetry measurements revealed highly negative first reduction potentials for the Mn[T pXPC]Ph series (~–0.95 V) as well as large electrochemical HOMO-LUMO gaps of ~1.7 V. The first reductions, however, are irreversible, suggesting cleavage of the Mn–Ph bond.« less

Continuous Isotropic-Nematic Transition in Amyloid Fibril Suspensions Driven by Thermophoresis.

PubMed

Vigolo, Daniele; Zhao, Jianguo; Handschin, Stephan; Cao, Xiaobao; deMello, Andrew J; Mezzenga, Raffaele

2017-04-27

The isotropic and nematic (I + N) coexistence for rod-like colloids is a signature of the first-order thermodynamics nature of this phase transition. However, in the case of amyloid fibrils, the biphasic region is too small to be experimentally detected, due to their extremely high aspect ratio. Herein, we study the thermophoretic behaviour of fluorescently labelled β-lactoglobulin amyloid fibrils by inducing a temperature gradient across a microfluidic channel. We discover that fibrils accumulate towards the hot side of the channel at the temperature range studied, thus presenting a negative Soret coefficient. By exploiting this thermophoretic behaviour, we show that it becomes possible to induce a continuous I-N transition with the I and N phases at the extremities of the channel, starting from an initially single N phase, by generating an appropriate concentration gradient along the width of the microchannel. Accordingly, we introduce a new methodology to control liquid crystal phase transitions in anisotropic colloidal suspensions. Because the induced order-order transitions are achieved under stationary conditions, this may have important implications in both applied colloidal science, such as in separation and fractionation of colloids, as well as in fundamental soft condensed matter, by widening the accessibility of target regions in the phase diagrams.

Chemically frozen multicomponent boundary layer theory of salt and/or ash deposition rates from combustion gases

NASA Technical Reports Server (NTRS)

Rosner, D. E.; Chen, B.-K.; Fryburg, G. C.; Kohl, F. J.

1979-01-01

There is increased interest in, and concern about, deposition and corrosion phenomena in combustion systems containing inorganic condensible vapors and particles (salts, ash). To meet the need for a computationally tractable deposition rate theory general enough to embrace multielement/component situations of current and future gas turbine and magnetogasdynamic interest, a multicomponent chemically 'frozen' boundary layer (CFBL) deposition theory is presented and its applicability to the special case of Na2SO4 deposition from seeded laboratory burner combustion products is demonstrated. The coupled effects of Fick (concentration) diffusion and Soret (thermal) diffusion are included, along with explicit corrections for effects of variable properties and free stream turbulence. The present formulation is sufficiently general to include the transport of particles provided they are small enough to be formally treated as heavy molecules. Quantitative criteria developed to delineate the domain of validity of CFBL-rate theory suggest considerable practical promise for the present framework, which is characterized by relatively modest demands for new input information and computer time.

Single step vacuum-free and hydrogen-free synthesis of graphene

NASA Astrophysics Data System (ADS)

Orellana, Christian; Cunha, Thiago; Fantini, Cristiano; Jaques, Alonso; Häberle, Patricio

2017-08-01

We report a modified method to grow graphene in a single-step process. It is based on chemical vapor deposition and considers the use of methane under extremely adverse synthesis conditions, namely in an open chamber without requiring the addition of gaseous hydrogen in any of the synthesis stages. The synthesis occurs between two parallel Cu plates, heated up via electromagnetic induction. The inductive heating yields a strong thermal gradient between the catalytic substrates and the surrounding environment, promoting the enrichment of hydrogen generated as fragments of the methane molecules within the volume confined by the Cu foils. This induced density gradient is due to thermo-diffusion, also known as the Soret effect. Hydrogen and other low mass molecular fractions produced during the process inhibit oxidative effects and simultaneously reduce the native oxide on the Cu surface. As a result, high quality graphene is obtained on the inner surfaces of the Cu sheets as confirmed by Raman spectroscopy.

The observation of spectral variation indicative of porphyrin biomarkers in reflectance spectra of source rock - The application of remote sensing technology to petroleum geochemistry

NASA Technical Reports Server (NTRS)

Holden, Peter Newhall; Gaffey, Michael J.

1990-01-01

The spectral signature of porphyrin compounds, considered to be biomarkers of depositional environment and thermal maturity, have been identified in reflectance spectra of oil shales. The key bands identified, in order of intensity, are the Soret (0.40 microns), alpha (0.57 microns), and beta (0.53 microns) bands. The observed bands represent the composite spectral signature of all porphyrin compounds present in the sample and, therefore, change position and intensity in accordance with changes in porphyrin chemistry.

Transport-induced shifts in condensate dew-point and composition in multicomponent systems with chemical reaction

NASA Technical Reports Server (NTRS)

Rosner, D. E.; Nagarajan, R.

1985-01-01

Partial heterogeneous condensation phenomena in multicomponent reacting systems are analyzed taking into consideration the chemical element transport phenomena. It is demonstrated that the dew-point surface temperature in chemically reactive systems is not a purely thermodynamic quantity, but is influenced by the multicomponent diffusion and Soret-mass diffusion phenomena. Several distinct dew-points are shown to exist in such systems and, as a result of transport constraints, the 'sharp' locus between two chemically distinct condensates is systematically moved to a difference mainstream composition.

Atmospheric neutral points outside of the principal plane. [points of vanished skylight polarization

NASA Technical Reports Server (NTRS)

Fraser, R. S.

1981-01-01

It is noted that the positions in the sky where the skylight is unpolarized, that is, the neutral points, are in most cases located in the vertical plane through the sun (the principal plane). Points have been observed outside the principal plane (Soret, 1888) when the plane intersected a lake or sea. Here, the neutral points were located at an azimuth of about 15 deg from the sun and near the almucantar through the sun. In order to investigate the effects of water surface and aerosols in the neutral point positions, the positions are computed for models of the earth-atmosphere system that simulate the observational conditions. The computed and measured positions are found to agree well. While previous observations provided only qualitative information on the degree of polarization, it is noted that the computations provide details concerning the polarization parameters.

Ytterbium-porphyrins as a new class of the luminescent labels

NASA Astrophysics Data System (ADS)

Tsvirko, M.; Korovin, Yu; Rusakova, N.

2007-08-01

New complexes of ytterbium with asymmetric porphyrins containing substituents in β-positions and hydrophobic meso-(monophenyl-p-oxypropyl)triphenylporphyrin (OPP) were obtained and characterized by elemental analysis, IR, UV-Vis absorption and luminescence spectroscopy. Electronic absorption, luminescence and luminescence excitation spectra of these complexes were studied at 295 K in DMF solutions and in the water-lecithin medium. The 4f-luminescence of ytterbium-porphyrins in the near infrared (IR) spectral region (λmax = 980 nm) is observed under excitation in Soret band (400-430 nm). The effect of substituent in porphyrin macroring on the 4f-luminescent properties was also investigated. The conjugates of these compounds with protein molecules - bovine serum albumin (BSA) were investigated as well. These compounds are interesting at the initial stage of diagnostics of tumor tissues as IR-luminescent probes due to their spectral-luminescent characteristics and some biochemical properties.

Isotope Fractionation by Diffusion in Liquids (Final Technical Report)

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

Richter, Frank

The overall objective of the DOE-funded research by grant DE-FG02-01ER15254 was document and quantify kinetic isotope fractionations during chemical and thermal (i.e., Soret) diffusion in liquids (silicate melts and water) and in the later years to include alloys and major minerals such as olivine and pyroxene. The research involved both laboratory experiments and applications to natural settings. The key idea is that major element zoning on natural geologic materials is common and can arise for either changes in melt composition during cooling and crystallization or from diffusion. The isotope effects associated with diffusion that we have documented are the keymore » for determining whether or not the zoning observed in a natural system was the result of diffusion. Only in those cases were the zoning is demonstrably due to diffusion can use independently measured rates of diffusion to constrain the thermal evolution of the system.« less

Solvent effects on the fluorescence and effective three-photon absorption of a Zn(II)-[meso-tetrakis(4-octyloxyphenyl)porphyrin

NASA Astrophysics Data System (ADS)

Wan, Yong; Xue, Yuxiong; Sheng, Ning; Rui, Guanghao; Lv, Changgui; He, Jun; Gu, Bing; Cui, Yiping

2018-06-01

The fluorescence and effective three-photon absorption (3PA) properties of Zn(II)-[meso-tetrakis(4-octyloxyphenyl)porphyrin] (labeled Zn(II)-porphyrin) dissolved in three different polar solvents were systematically investigated. The electrochemical and photophysical properties of Zn(II)-porphyrin were investigated by 1H NMR spectra, IR spectra, mass spectroscopy, and electronic absorption spectra. The fluorescence emission of Zn(II)-porphyrin in three different solvents excited at the wavelengths of 420 nm (Soret band) and 550 nm (Q-band) were analyzed. By performing Z-scan experiments with femtosecond laser pulses at a wavelength of 800 nm, the effective 3PA process of Zn(II)-porphyrin in three different solvents was observed and the underlying mechanism was discussed in detail. It is found that the fluorescence spectra slightly depend on the polarity of the solvent. Interestingly, the effective 3PA properties of Zn(II)-porphyrin strongly depend on the solvent polarity. The lower the solvent polarity is, the larger effective 3PA cross-section is. Low polar solvents are beneficial to applications of Zn(II)-porphyrin in optical limiting, photodynamic therapy, etc.

Effects of Visible Irradiation of Protoporphyrin IX on the Self Assembly of Tubulin Heterodimers

PubMed Central

Sagarra, Alicia Vall; McMicken, Brady; Nonell, Santi; Brancaleon, Lorenzo

2016-01-01

The formation and the effects of the laser irradiation of the complex formed by protoporphyrin IX (PPIX) and tubulin was investigated. We have used tubulin as a model protein to investigate whether docked photoactive ligands can affect the structure and function of polypeptides upon exposure to visible light. We observed that laser irradiation in the Soret band prompts bleaching of the PPIX which is accompanied by a sharp decrease in the intensity and average fluorescence lifetime of the protein (dominated by the four tryptophan residues of the tubulin monomer). The kinetics indicate non-trivial effects and suggest that the photosensitization of the PPIX bound to tubulin prompts structural alterations of the protein. These modifications were also observed through changes in the energy transfer between Trp residues and PPIX. The result suggest that laser irradiation produces localized partial unfolding of tubulin and that the changes prompt modification of the formation of microtubules in vitro. Measurements of singlet oxygen formation were inconclusive in determining whether the changes are prompted by reactive oxygen species or other excited state mechanisms. PMID:27490308

Dianionic Titanyl and Vanadyl (Cation+ )2 [MIV O(Pc4- )]2- Phthalocyanine Salts Containing Pc4- Macrocycles.

PubMed

Konarev, Dmitri V; Kuzmin, Alexey V; Khasanov, Salavat S; Litvinov, Alexey L; Otsuka, Akihiro; Yamochi, Hideki; Kitagawa, Hiroshi; Lyubovskaya, Rimma N

2018-06-18

In this study, the titanyl and vanadyl phthalocyanine (Pc) salts (Bu 4 N + ) 2 [M IV O(Pc 4- )] 2- (M=Ti, V) and (Bu 3 MeP + ) 2 [M IV O(Pc 4- )] 2- (M=Ti, V) with [M IV O(Pc 4- )] 2- dianions were synthesized and characterized. Reduction of M IV O(Pc 2- ) carried out with an excess of sodium fluorenone ketyl in the presence of Bu 4 N + or Bu 3 MeP + is exclusive to the phthalocyanine centers, forming Pc 4- species. During reduction, the metal +4 charge did not change, implying that Pc is an non-innocent ligand. The Pc negative charge increase caused the C-N(pyr) bonds to elongate and the C-N(imine) bonds to alternate, thus increasing the distortion of Pc. Jahn-Teller effects are significant in the [eg(π*)] 2 dianion ground state and can additionally distort the Pc macrocycles. Blueshifts of the Soret and Q-bands were observed in the UV/Vis/NIR when M IV O(Pc 2- ) was reduced to [M IV O(Pc . 3- )] . - and [M IV O(Pc 4- )] 2- . From magnetic measurements, [Ti IV O(Pc 4- )] 2- was found to be diamagnetic and (Bu 4 N + ) 2 [V IV O(Pc 4- )] 2- and (Bu 3 MeP + ) 2 [V IV O(Pc 4- )] 2- were found to have magnetic moments of 1.72-1.78 μ B corresponding to an S=1/2 spin state owing to V IV electron spin. As a result, two latter salts show EPR signals with V IV hyperfine coupling. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structure and Reactivity of a Thermostable Prokaryotic Nitric-oxide Synthase That Forms a Long-lived Oxy-Heme Complex

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

Sudhamsu,J.; Crane, B.

2006-01-01

In an effort to generate more stable reaction intermediates involved in substrate oxidation by nitric-oxide synthases (NOSs), we have cloned, expressed, and characterized a thermostable NOS homolog from the thermophilic bacterium Geobacillus stearothermophilus (gsNOS). As expected, gsNOS forms nitric oxide (NO) from L-arginine via the stable intermediate N-hydroxy L-arginine (NOHA). The addition of oxygen to ferrous gsNOS results in long-lived heme-oxy complexes in the presence (Soret peak 427 nm) and absence (Soret peak 413 nm) of substrates L-arginine and NOHA. The substrate-induced red shift correlates with hydrogen bonding between substrate and heme-bound oxygen resulting in conversion to a ferric heme-superoxymore » species. In single turnover experiments with NOHA, NO forms only in the presence of H4B. The crystal structure of gsNOS at 3.2 A Angstroms of resolution reveals great similarity to other known bacterial NOS structures, with the exception of differences in the distal heme pocket, close to the oxygen binding site. In particular, a Lys-356 (Bacillus subtilis NOS) to Arg-365 (gsNOS) substitution alters the conformation of a conserved Asp carboxylate, resulting in movement of an Ile residue toward the heme. Thus, a more constrained heme pocket may slow ligand dissociation and increase the lifetime of heme-bound oxygen to seconds at 4 degC. Similarly, the ferric-heme NO complex is also stabilized in gsNOS. The slow kinetics of gsNOS offer promise for studying downstream intermediates involved in substrate oxidation.« less

Adsorption characteristics of a cationic porphyrin on nanoclay at various pH.

PubMed

Rice, Zachary; Bergkvist, Magnus

2009-07-15

Natural and synthetic porphyrin derivatives offer a range of applications including enzymatic catalysis, photosensitizers for light harvesting and chemical reactions, and molecular electronics. They exhibit unique optical spectra dominated by the presence of Soret and Q-band structures whose position and shape offer a straightforward method to characterize porphyrins in various surroundings. In many applications it is often beneficial to have porphyrins adsorbed onto a solid matrix. Applications of porphyrin-clay complexes extend to numerous biological applications including pharmaceutical drug delivery, cosmetics, and agricultural applications and thus a full understanding of porphyrin-clay surface interactions are essential. Here we investigated the adsorption behavior of meso-tetra(4-N,N,N-trimethylanilinium) porphine (TMAP) onto sodium containing, natural montmorillonite clay (Cloisite Na(+)) in characteristic biological buffers over a range of pHs (approximately 2-9). Spectroscopic analyses show a linear absorption response at acidic and basic pHs but a slight deviation at intermediate pHs. Absorption spectra for TMAP on clay showed distinct red shifts of the Soret and Q-bands compared to free TMAP for all buffer conditions indicating core pi-electron delocalization into the substituent rings. At intermediate pHs, a gradual transition between protonated/deprotonated states were seen, presumably due to higher H(+) concentration at the surface than in bulk. Results indicate TMAP adsorption to clay occurs in a monolayer fashion at low/high pH while slightly acidic/neutral pH possibly rearrange on the surface and/or form aggregates. AFM images of clay saturated with TMAP are reported and show single isolated clay sheets without aggregation, similar to clay without TMAP.

Simplified procedure for encapsulating cytochrome c in silica aerogel nanoarchitectures while retaining gas-phase bioactivity.

PubMed

Harper-Leatherman, Amanda S; Iftikhar, Mariam; Ndoi, Adela; Scappaticci, Steven J; Lisi, George P; Buzard, Kaitlyn L; Garvey, Elizabeth M

2012-10-16

Cytochrome c (cyt. c) has been encapsulated in silica sol-gels and processed to form bioaerogels with gas-phase activity for nitric oxide through a simplified synthetic procedure. Previous reports demonstrated a need to adsorb cyt. c to metal nanoparticles prior to silica sol-gel encapsulation and processing to form aerogels. We report that cyt. c can be encapsulated in aerogels without added nanoparticles and retain structural stability and gas-phase activity for nitric oxide. While the UV-visible Soret absorbance and nitric oxide response indicate that cyt. c encapsulated with nanoparticles in aerogels remains slightly more stable and functional than cyt. c encapsulated alone, these properties are not very different in the two types of aerogels. From UV-visible and Soret circular dichroism results, we infer that cyt. c encapsulated alone self-organizes to reduce contact with the silica gel in a way that may bear at least some resemblance to the way cyt. c self-organizes into superstructures of protein within aerogels when nanoparticles are present. Both the buffer concentration and the cyt. c concentration of solutions used to synthesize the bioaerogels affect the structural integrity of the protein encapsulated alone within the dried aerogels. Optimized bioaerogels are formed when cyt. c is encapsulated from 40 mM phosphate buffered solutions, and when the loaded cyt. c concentration in the aerogel is in the range of 5 to 15 μM. Increased viability of cyt. c in aerogels is also observed when supercritical fluid used to produce aerogels is vented over relatively long times.

Problems in Catalytic Oxidation of Hydrocarbons and Detailed Simulation of Combustion Processes

NASA Astrophysics Data System (ADS)

Xin, Yuxuan

This dissertation research consists of two parts, with Part I on the kinetics of catalytic oxidation of hydrocarbons and Part II on aspects on the detailed simulation of combustion processes. In Part I, the catalytic oxidation of C1--C3 hydrocarbons, namely methane, ethane, propane and ethylene, was investigated for lean hydrocarbon-air mixtures over an unsupported Pd-based catalyst, from 600 to 800 K and under atmospheric pressure. In Chapter 2, the experimental facility of wire microcalorimetry and simulation configuration were described in details. In Chapter 3 and 4, the oxidation rate of C1--C 3 hydrocarbons is demonstrated to be determined by the dissociative adsorption of hydrocarbons. A detailed surface kinetics model is proposed with deriving the rate coefficient of hydrocarbon dissociative adsorption from the wire microcalorimetry data. In Part II, four fundamental studies were conducted through detailed combustion simulations. In Chapter 5, self-accelerating hydrogen-air flames are studied via two-dimensional detailed numerical simulation (DNS). The increase in the global flame velocity is shown to be caused by the increase of flame surface area, and the fractal structure of the flame front is demonstrated by the box-counting method. In Chapter 6, skeletal reaction models for butane combustion are derived by using directed relation graph (DRG) and DRG-aided sensitivity analysis (DRGASA), and uncertainty minimization by polynomial chaos expansion (MUM-PCE) mothodes. The dependence of model uncertainty is subjected to the completeness of the model. In Chapter 7, a systematic strategy is proposed to reduce the cost of the multicomponent diffusion model by accurately accounting for the species whose diffusivity is important to the global responses of the combustion systems, and approximating those of less importance by the mixture-averaged model. The reduced model is validated in an n-heptane mechanism with 88 species. In Chapter 8, the influence of Soret diffusion on the n-heptane/air flames is investigated numerically. In the unstretched flames, Soret diffusion primarily affects the chemical kinetics embedded in the flame structure and the net effect is small; while in the stretched flames, its impact is mainly through those of n-heptane and the secondary fuel, H2, in modifying the flame temperature, with substantial effects.

A biophysical investigation on the binding of proflavine with human hemoglobin: Insights from spectroscopy, thermodynamics and AFM studies.

PubMed

Basu, Anirban; Kumar, Gopinatha Suresh

2016-12-01

Interaction of proflavine with hemoglobin (Hgb) was studied employing spectroscopy, calorimetry, and atomic force microscopy. The equilibrium constant was found to be of the order 10 4 M -1 . The quenching of Hgb fluorescence by proflavine was due to the complex formation. Calculation of the molecular distance (r) between the donor (β-Trp37 of Hgb) and acceptor (proflavine) suggested that energy can be efficiently transferred from the β-Trp37 residue at the α1β2 interface of the protein to the dye. Proflavine induced significant secondary structural changes in Hgb. Synchronous fluorescence studies showed that proflavine altered the microenvironment around the tryptophan residues to a greater extent than the tyrosine residues. Circular dichroism spectral studies showed that proflavine caused significant reduction in the α-helical content of Hgb. The esterase activity assay further complemented the circular dichroism data. The Soret band intensity of Hgb decreased upon complexation. Differential scanning calorimetry and circular dichroism melting results revealed that proflavine induced destabilization of Hgb. The binding was driven by both positive entropy and negative enthalpy. Atomic force microscopy studies revealed that the essential morphological features of hemoglobin were retained in the presence of proflavine. Overall, insights on the photophysical aspects and energetics of the binding of proflavine with Hgb are presented. Copyright © 2016 Elsevier B.V. All rights reserved.

Thermodiffusion in concentrated ferrofluids: A review and current experimental and numerical results on non-magnetic thermodiffusion

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

Sprenger, Lisa, E-mail: Lisa.Sprenger@tu-dresden.de; Lange, Adrian; Odenbach, Stefan

2013-12-15

Ferrofluids are colloidal suspensions consisting of magnetic nanoparticles dispersed in a carrier liquid. Their thermodiffusive behaviour is rather strong compared to molecular binary mixtures, leading to a Soret coefficient (S{sub T}) of 0.16 K{sup −1}. Former experiments with dilute magnetic fluids have been done with thermogravitational columns or horizontal thermodiffusion cells by different research groups. Considering the horizontal thermodiffusion cell, a former analytical approach has been used to solve the phenomenological diffusion equation in one dimension assuming a constant concentration gradient over the cell's height. The current experimental work is based on the horizontal separation cell and emphasises the comparison ofmore » the concentration development in different concentrated magnetic fluids and at different temperature gradients. The ferrofluid investigated is the kerosene-based EMG905 (Ferrotec) to be compared with the APG513A (Ferrotec), both containing magnetite nanoparticles. The experiments prove that the separation process linearly depends on the temperature gradient and that a constant concentration gradient develops in the setup due to the separation. Analytical one dimensional and numerical three dimensional approaches to solve the diffusion equation are derived to be compared with the solution used so far for dilute fluids to see if formerly made assumptions also hold for higher concentrated fluids. Both, the analytical and numerical solutions, either in a phenomenological or a thermodynamic description, are able to reproduce the separation signal gained from the experiments. The Soret coefficient can then be determined to 0.184 K{sup −1} in the analytical case and 0.29 K{sup −1} in the numerical case. Former theoretical approaches for dilute magnetic fluids underestimate the strength of the separation in the case of a concentrated ferrofluid.« less

Tetrabenzoporphyrin and -mono-, -cis-di- and Tetrabenzotriazaporphyrin Derivatives: Electrochemical and Spectroscopic Implications of meso CH Group Replacement with Nitrogen.

PubMed

van As, Adele; Joubert, Chris C; Buitendach, Blenerhassitt E; Erasmus, Elizabeth; Conradie, Jeanet; Cammidge, Andrew N; Chambrier, Isabelle; Cook, Michael J; Swarts, Jannie C

2015-06-01

Nonperipherally hexyl-substituted metal-free tetrabenzoporphyrin (2H-TBP, 1a) tetrabenzomonoazaporphyrin (2H-TBMAP, 2a), tetrabenzo-cis-diazaporphyrin (2H-TBDAP, 3a), tetrabenzotriazaporphyrin (2H-TBTAP, 4a), and phthalocyanine (2H-Pc, 5a), as well as their copper complexes (1b-5b), were synthesized. As the number of meso nitrogen atoms increases from zero to four, λmax of the Q-band absorption peak becomes red-shifted by almost 100 nm, and extinction coefficients increased at least threefold. Simultaneously the blue-shifted Soret (UV) band substantially decreased in intensity. These changes were related to the relative electron-density of each macrocycle expressed as the group electronegativity sum of all meso N and CH atom groups, ∑χR. X-ray photoelectron spectroscopy differentiated between the three different types of macrocyclic nitrogen atoms (the Ninner, (NH)inner, and Nmeso) in the metal-free complexes. Binding energies of the Nmeso and Ninner,Cu atoms in copper chelates could not be resolved. Copper insertion lowered especially the cathodic redox potentials, while all four observed redox processes occurred at larger potentials as the number of meso nitrogens increased. Computational chemical methods using density functional theory confirmed 1b to exhibit a Cu(II) reduction prior to ring-based reductions, while for 2b, Cu(II) reduction is the first reductive step only if the nonperipheral substituents are hydrogen. When they are methyl groups, it is the second reduction process; when they are ethyl, propyl, or hexyl, it becomes the third reductive process. Spectro-electrochemical measurements showed redox processes were associated with a substantial change in intensity of at least two main absorbances (the Q and Soret bands) in the UV spectra of these compounds.

The Prediction of Nozzle Performance and Heat Transfer in Hydrogen/Oxygen Rocket Engines with Transpiration Cooling, Film Cooling, and High Area Ratios

NASA Technical Reports Server (NTRS)

Kacynski, Kenneth J.; Hoffman, Joe D.

1994-01-01

An advanced engineering computational model has been developed to aid in the analysis of chemical rocket engines. The complete multispecies, chemically reacting and diffusing Navier-Stokes equations are modelled, including the Soret thermal diffusion and Dufour energy transfer terms. Demonstration cases are presented for a 1030:1 area ratio nozzle, a 25 lbf film-cooled nozzle, and a transpiration-cooled plug-and-spool rocket engine. The results indicate that the thrust coefficient predictions of the 1030:1 nozzle and the film-cooled nozzle are within 0.2 to 0.5 percent, respectively, of experimental measurements. Further, the model's predictions agree very well with the heat transfer measurements made in all of the nozzle test cases. It is demonstrated that thermal diffusion has a significant effect on the predicted mass fraction of hydrogen along the wall of the nozzle and was shown to represent a significant fraction of the diffusion fluxes occurring in the transpiration-cooled rocket engine.

Selenolate Complexes of CYP101 and the Heme-bound hHO-1/H25A Proximal Cavity Mutant

PubMed Central

Jiang, Yongying; Ortiz de Montellano, Paul R.

2009-01-01

Thiolate and selenolate complexes of CYP101 (P450cam) and the H25A proximal cavity mutant of heme-bound human heme oxygenase-1 (hHO-1) have been examined by UV-visible spectroscopy. Both thiolate and selenolate ligands bound to the heme distal side in CYP101 and gave rise to characteristic hyperporphyrin spectra. Thiolate ligands also bound to the proximal side of the heme in the cavity created by the H25A mutation in hHO-1, giving a Soret absorption similar to that of the H25C hHO-1 mutant. Selenolate ligands also bound to this cavity mutant under anaerobic conditions, but reduced the heme iron to the ferrous state as shown by formation of a ferrous-CO complex. Under aerobic conditions, the selenolate but not thiolate ligand was rapidly oxidized. These results indicate that selenocysteine-coordinated heme proteins will not be stable species in the absence of a redox potential stabilizing effect. PMID:18376820

Selenolate complexes of CYP101 and the heme-bound hHO-1/H25A proximal cavity mutant.

PubMed

Jiang, Yongying; Ortiz de Montellano, Paul R

2008-05-05

Thiolate and selenolate complexes of CYP101 (P450cam) and the H25A proximal cavity mutant of heme-bound human heme oxygenase-1 (hHO-1) have been examined by UV-vis spectroscopy. Both thiolate and selenolate ligands bound to the heme distal side in CYP101 and gave rise to characteristic hyperporphyrin spectra. Thiolate ligands also bound to the proximal side of the heme in the cavity created by the H25A mutation in hHO-1, giving a Soret absorption similar to that of the H25C hHO-1 mutant. Selenolate ligands also bound to this cavity mutant under anaerobic conditions but reduced the heme iron to the ferrous state, as shown by the formation of a ferrous CO complex. Under aerobic conditions, the selenolate ligand but not the thiolate ligand was rapidly oxidized. These results indicate that selenocysteine-coordinated heme proteins will not be stable species in the absence of a redox potential stabilizing effect.

Thermo-Osmotic Flow in Thin Films.

PubMed

Bregulla, Andreas P; Würger, Alois; Günther, Katrin; Mertig, Michael; Cichos, Frank

2016-05-06

We report on the first microscale observation of the velocity field imposed by a nonuniform heat content along the solid-liquid boundary. We determine both radial and vertical velocity components of this thermo-osmotic flow field by tracking single tracer nanoparticles. The measured flow profiles are compared to an approximate analytical theory and to numerical calculations. From the measured slip velocity we deduce the thermo-osmotic coefficient for both bare glass and Pluronic F-127 covered surfaces. The value for Pluronic F-127 agrees well with Soret data for polyethylene glycol, whereas that for glass differs from literature values and indicates the complex boundary layer thermodynamics of glass-water interfaces.

Investigation of human serum albumin (HSA) binding specificity of certain photosensitizers related to pyropheophorbide-a and bacteriopurpurinimide by circular dichroism spectroscopy and its correlation with in vivo photosensitizing efficacy.

PubMed

Chen, Yihui; Miclea, Razvan; Srikrishnan, Thamarapu; Balasubramanian, Sathyamangalam; Dougherty, Thomas J; Pandey, Ravindra K

2005-07-01

A series of pyropheophorbide-a and bacteriopurpurinimides were investigated to understand the correlation between HSA (site II) binding affinity and in vivo photosensitizing activity. In our study, photosensitizers that bound to site II of HSA produced a significant difference in the circular dichroism spectra of the corresponding complexes, especially at Soret band region of the photosensitizers. Our results suggest that CD spectroscopy of the photosensitizer-HSA complexes could be a valuable tool in screening new photosensitizers before evaluating them for in vivo efficacy.

Cyclo[n]pyrroles and methods thereto

DOEpatents

Sessler, Jonathan L.; Seidel, Daniel; Bolze, Frederic R.; Koehler, Thomas

2006-01-10

The present invention provides an oxidative coupling procedure that allows efficient synthesis of novel cyclo[n]pyrrole macrocycles. Therefore, the present invention provides cyclo[n]pyrroles where n is 6, 7, 8, 9, 10, 11, or 12, and derivatives, multimers, isomers, and ion and neutral molecule complexes thereof as new compositions of matter. A protonated form of cyclo[n]pyrrole displays a gap of up to 700 nm between strong Soret and Q-like absorption bands in the electronic spectrum, demonstrating no significant ground state absorption in the visible portion of the electronic spectrum. Uses of cyclo[n]pyrroles as separation media, nonlinear optical materials, information storage media and infrared filters are provided.

Student Outreach With Renewable Energy Technology

NASA Technical Reports Server (NTRS)

Clark, Eric B. (Technical Monitor); Buffinger, D.; Fuller, C.; Kalu, A.

2003-01-01

The Student Outreach with Renewable Energy Technology (SORET) program is a joint grant that involves a collaboration between three HBCU's (Central State University, Savannah State University, and Wilberforce University) and NASA John H. Glenn Research Center at Lewis Field. The overall goal of the grant is to increase the interest of minority students in the technical disciplines, to encourage participating minority students to continue their undergraduate study in these disciplines, and to promote graduate school to these students. As a part of SORET, Central State University has developed an undergraduate research associates program over the past two years. As part of this program, students are required to take special laboratory courses offered at Wilberforce University that involve the application of renewable energy systems. The course requires the students to design, construct, and install a renewable energy project. In addition to the applied renewable energy course, Central State University provided four undergraduate research associates the opportunity to participate in summer internships at Texas Southern University (Renewable Energy Environmental Protection Program) and the Cleveland African-American Museum (Renewable Energy Summer Camp for High School Students) an activity co sponsored by NASA and the Cleveland African-American Museum. Savannah State University held a high school summer program with a theme of the Direct Impact of Science on Our Every Day Lives. The purpose of the institute was to whet the interest of students in science, mathematics, engineering, and technology (SMET) by demonstrating the effectiveness of science to address real world problems. The 2001 institute involved the design and installation of a PV water pumping system at the Center for Advanced Water Technology and Energy Systems at Savannah State. Both high school students and undergraduates contributed to this project. Wilberforce University has used NASA support to provide resources for an Applied Renewable Energy Laboratory offered to both Central State and Wilberforce students. In addition, research endeavors for high school and undergraduates were funded during the summer. The research involved attempts to layer photovoltaic materials on a conducting polymer (polypyrrole) substrate. Two undergraduate students who were interested in polymer research originated this concept. Finally, the university was able to purchase a meteorological station to assist in the analysis of the solar/wind hybrid power system operating at the university.

Vibrational coherence in polar solutions of Zn(II) tetrakis(N-methylpyridyl)porphyrin with Soret-band excitation: rapidly damped intermolecular modes with clustered solvent molecules and slowly damped intramolecular modes from the porphyrin macrocycle.

PubMed

Dillman, Kevin L; Shelly, Katherine R; Beck, Warren F

2009-04-30

Ground-state coherent wavepacket motions arising from intermolecular modes with clustered, first-shell solvent molecules were observed using the femtosecond dynamic absorption technique in polar solutions of Zn(II) meso-tetrakis(N-methylpyridyl)porphyrin (ZnTMPyP) with excitation in the Soret absorption band. As was observed previously in bacteriochlorophyll a solution, the pump-probe transients in ZnTMPyP solutions are weakly modulated by slowly damped (effective damping time gamma > 1 ps) features that are assigned to intramolecular modes, the skeletal normal modes of vibration of the porphyrin. The 40 cm(-1) and 215 cm(-1) modes from the metal-doming and metal-solvent-ligand modes, respectively, are members of this set of modulation components. A slowly damped 2-4 cm(-1) component is assigned to the internal rotation of the N-methylpyridyl rings with respect to the porphyrin macrocycle; this mode obtains strong resonance Raman intensity enhancement from an extensive delocalization of pi-electron density from the porphyrin in the ground state onto the rings in the pi* excited states. The dominant features observed in the pump-probe transients are a pair of rapidly damped (gamma < 250 fs) modulation components arising from intermolecular modes with solvent molecules. This structural assignment is supported by an isotope-dependent shift of the average mode frequencies in methanol and perdeuterated methanol. The solvent dependence of the mean intermolecular mode frequency is consistent with a van der Waals intermolecular potential that has significant contributions only from the London dispersion and induction interactions; ion-dipole or ion-induced-dipole terms do not make large contributions because the pi-electron density is not extensively delocalized onto the N-methylpyridyl rings. The modulation depth associated with the intermolecular modes exhibits a marked dependence on the electronic structure of the solvent that is probably related to the degree of covalency; the strongest modulations are observed in acetonitrile and dimethylsulfoxide. The results strongly support a structural assignment of the low-frequency modes that are coupled to the primary and secondary electron-transfer reactions in photosynthetic reaction centers to intermolecular modes between the redox-active chromophores and first-solvation shell groups from the surrounding protein, and an important additional function of the intermolecular modes in the stabilization of charged intermediates is suggested.

Stability of exact solutions describing two-layer flows with evaporation at the interface

NASA Astrophysics Data System (ADS)

Bekezhanova, V. B.; Goncharova, O. N.

2016-12-01

A new exact solution of the equations of free convection has been constructed in the framework of the Oberbeck-Boussinesq approximation of the Navier-Stokes equations. The solution describes the joint flow of an evaporating viscous heat-conducting liquid and gas-vapor mixture in a horizontal channel. In the gas phase the Dufour and Soret effects are taken into account. The consideration of the exact solution allows one to describe different classes of flows depending on the values of the problem parameters and boundary conditions for the vapor concentration. A classification of solutions and results of the solution analysis are presented. The effects of the external disturbing influences (of the liquid flow rates and longitudinal gradients of temperature on the channel walls) on the stability characteristics have been numerically studied for the system HFE7100-nitrogen in the common case, when the longitudinal temperature gradients on the boundaries of the channel are not equal. In the system both monotonic and oscillatory modes can be formed, which damp or grow depending on the values of the initial perturbations, flow rates and temperature gradients. Hydrodynamic perturbations are most dangerous under large gas flow rates. The increasing oscillatory perturbations are developed due to the thermocapillary effect under large longitudinal gradients of temperature. The typical forms of the disturbances are shown.

Reaction of tin(iv) phthalocyanine dichloride with decamethylmetallocenes (M = CrII and CoII). Strong magnetic coupling of spins in (Cp*2Co+){SnIVCl2(Pc˙3-)}˙-·2C6H4Cl2.

PubMed

Konarev, Dmitri V; Troyanov, Sergey I; Shestakov, Alexander F; Yudanova, Evgeniya I; Otsuka, Akihiro; Yamochi, Hideki; Kitagawa, Hiroshi; Lyubovskaya, Rimma N

2018-01-23

The reaction of tin(iv) phthalocyanine dichloride {Sn IV Cl 2 (Pc 2- )} with decamethylmetallocenes (Cp* 2 M, M = Co, Cr) has been studied. Decamethylcobaltocene reduces Sn IV Cl 2 (Pc 2- ) to form the (Cp* 2 Co + ){Sn IV Cl 2 (Pc˙ 3- )}˙ - ·2C 6 H 4 Cl 2 (1) complex. The negative charge of {Sn IV Cl 2 (Pc˙ 3- )}˙ - is delocalized over the Pc macrocycle providing the alternation of the C-N(imine) bonds, the appearance of new bands in the NIR range and a strong blue shift of both the Soret and Q-bands in the spectrum of 1. The magnetic moment of 1 is equal to 1.68μ B at 300 K, indicating the contribution of one S = 1/2 spin of the Pc˙ 3- macrocycles. These macrocycles form closely packed double stacks in 1 with effective π-π interactions providing strong antiferromagnetic coupling of spins at a Weiss temperature of -80 K. Decamethylchromocene initially also reduces Sn IV Cl 2 (Pc 2- ) to form the [(Cp* 2 Cr + ){Sn VI Cl 2 (Pc˙ 3- )}˙ - complex but further reaction between the ions is observed. This reaction is accompanied by the substitution of one Cp* ligand of Cp* 2 Cr by chloride anions originating from {Sn IV Cl 2 (Pc˙ 3- )}˙ - to form the complex {(Cp*CrCl 2 )(Sn IV (μ-Cl)(Pc 2- ))}·C 6 H 4 Cl 2 (2) in which the (Cp*CrCl 2 ) and {Sn IV (Pc 2- )} species are bonded through the μ-bridged Cl - anion. According to the DFT calculations, this reaction proceeds via an intermediate [(Cp* 2 CrCl)(SnClPc)] complex.

Hydrogen bond controlled adduct formation of meso-tetra(4-sulfonatophenyl)porphyrin with protic acids: a UV-vis spectroscopic study.

PubMed

Zakavi, Saeed; Rahiminezhad, Hajar; Alizadeh, Robabeh

2010-12-01

Interaction of meso-tetra(4-sulfonatophenyl)porphyrin (H2tppS4) with weak and strong protic acid have been studied by UV-vis spectroscopy in water, dichloromethane and methanol. Different shifts of the Soret and Q(0,0) bands in the three solvents, the aggregation of diprotonated species and the stability of porphyrin-acid adducts in the solution, may be explained by the inter- and intramolecular hydrogen bonds. Whilst, the addition of excess amounts of tetra-n-butylammonium chloride to H2tppS4(Cl)2 in dichloromethane has little to no effect on the UV-vis spectrum of the dication, gradual addition of tetra-n-butylammonium hydrogen sulfate to the dichloromethane solution of H2tppS4(H2SO4)2 leads to the degradation of adducts and the release of porphryin. The results of this study clearly show the crucial role played by hydrogen bonds between the porphyrin diprotonated species and the counter ion in the stability of porphyrin diacids in solution. Copyright © 2010 Elsevier B.V. All rights reserved.

Rheological Properties of Quasi-2D Fluids in Microgravity

NASA Technical Reports Server (NTRS)

Trittel, Torsten; Stannarius, Ralf; Eremin, Alexey; Harth, Kirsten; Clark, Noel A.; Maclennan, Joseph; Glaser, Matthew; Park, Cheol; Hall, Nancy; Tin, Padetha

2016-01-01

Freely suspended smectic films of sub-micrometer thickness and lateral extensions of several millimeters are used to study thermally driven convection and diffusion in the film plane. The experiments were performed during a six minute microgravity phase of a TEXUS suborbital rocket flight (Texus 52, launched April 27, 2015). The project served as a preliminary test for a planned ISS Experiment with liquid crystal films (OASIS), and in addition it provided new experimental data on smectic films exposed to in-plane thermal gradients.We find an attraction of the smectic material towards the cold edge of the film in a temperature gradient, similar to a Soret effect. This process is reversed when this edge is heated up again. Thermal convection driven by two thermocontacts in the film is practically absent, even at temperature gradients up to 10 Kmm, thermally driven convection sets in when the hot post reaches the transition temperature to the nematic phase.An additional experiment was performed under microgravity conditions to test the stability of liquid crystal bridges in different smectic phases.

Real-Gas Effects on Binary Mixing Layers

NASA Technical Reports Server (NTRS)

Okong'o, Nora; Bellan, Josette

2003-01-01

This paper presents a computational study of real-gas effects on the mean flow and temporal stability of heptane/nitrogen and oxygen/hydrogen mixing layers at supercritical pressures. These layers consist of two counterflowing free streams of different composition, temperature, and density. As in related prior studies reported in NASA Tech Briefs, the governing conservation equations were the Navier-Stokes equations of compressible flow plus equations for the conservation of total energy and of chemical- species masses. In these equations, the expressions for heat fluxes and chemical-species mass fluxes were derived from fluctuation-dissipation theory and incorporate Soret and Dufour effects. Similarity equations for the streamwise velocity, temperature, and mass fractions were derived as approximations to the governing equations. Similarity profiles showed important real-gas, non-ideal-mixture effects, particularly for temperature, in departing from the error-function profile, which is the similarity solution for incompressible flow. The temperature behavior was attributed to real-gas thermodynamics and variations in Schmidt and Prandtl numbers. Temporal linear inviscid stability analyses were performed using the similarity and error-function profiles as the mean flow. For the similarity profiles, the growth rates were found to be larger and the wavelengths of highest instability shorter, relative to those of the errorfunction profiles and to those obtained from incompressible-flow stability analysis. The range of unstable wavelengths was found to be larger for the similarity profiles than for the error-function profiles

Does thermophoresis reduce aggregate stability?

NASA Astrophysics Data System (ADS)

Sachs, Eyal; Sarah, Pariente

2017-04-01

Thermophoresis is mass flow driven by a thermal gradient. As a result of Seebeck effect and Soret effect, colloids can move from the hot to the cold region or vice versa, depending on the electrolyte composition and on the particle size. This migration of colloids can weaken aggregates. The effect of raindrop temperatures on runoff generation and erosion on clayey soil was investigated in sprinkling experiments with a laboratory rotating disk rain simulator. The experiments were applied to Rhodoxeralt (Terra Rossa) soil with two pre-prepared moisture contents: hygroscopic and field capacity. For each moisture content three rainfall temperatures were applied: 2, 20, and 35°C. Erosion was generally lower in the pre-wetted soil than in the dry soil (12.5 and 24.4 g m-2 per 40 mm of rain,respectively). Whereas there was no significant effect of raindrop temperature on the dry soil the soil that was pre-moistened to field capacity was affected by rainwater temperature: runoff and erosion were high when the temperature difference between rainfall and soil surface was high, sediment yields were 13.9, 5.2, and 18.3 g m-2 per 40 mm of rain, for rain temperature of 2, 20, and 35 °C, respectively. It is reasonable to conclude that thermophoresis caused by thermal gradients within the soil solution reduces the stability of aggregates and then increase the soil losses.

Contribution to the benchmark for ternary mixtures: Transient analysis in microgravity conditions.

PubMed

Ahadi, Amirhossein; Ziad Saghir, M

2015-04-01

We present a transient experimental analysis of the DCMIX1 project conducted onboard the International Space Station for a ternary tetrahydronaphtalene, isobutylbenzene, n-dodecane mixture. Raw images taken in microgravity environment using the SODI (Selectable Optical Diagnostic) apparatus which is equipped with two wavelength diagnostic were processed and the results were analyzed in this work. We measured the concentration profile of the mixture containing 80% THN, 10% IBB and 10% nC12 during the entire experiment using an advanced image processing technique and accordingly we determined the Soret coefficients using an advanced curve-fitting and post-processing technique. It must be noted that the experiment has been repeated five times to ensure the repeatability of the experiment.

Photoswitchable Sn-Cyt c Solid-State Devices.

PubMed

Nakamaru, Satoshi; Scholz, Frank; Ford, William E; Goto, Yoshio; von Wrochem, Florian

2017-06-01

Electron transfer across proteins plays an important role in many biological processes, including those relevant for the conversion of solar photons to chemical energy. Previous studies demonstrated the generation of photocurrents upon light irradiation in a number of photoactive proteins, such as photosystem I or bacteriorhodopsin. Here, it is shown that Sn-cytochrome c layers act as reversible and efficient photoelectrochemical switches upon integration into large-area solid-state junctions. Photocurrents are observed both in the Soret band (λ = 405 nm) and in the Q band (λ = 535 nm), with current on/off ratios reaching values of up to 25. The underlying modulation in charge-transfer rate is attributed to a hole-transport channel created by the photoexcitation of the Sn-porphyrin. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The growth of metastable peritectic compounds

NASA Technical Reports Server (NTRS)

Larson, D. J., Jr.; Pirich, R. G.

1981-01-01

The influence of gravitationally driven thermosolutal convection on the directional solidification of peritectic alloys is considered as well as the relationships between the solidification processing conditions, and the microstructure, chemistry, and magnetic properties of such alloys. Analysis of directionally solidified Pb-Bi peritectic samples indicates that appreciable macrosegregation occurs due to thermosolutal convection and/or Soret diffusion. A peritectic solidification model which accounts for partial mixing in the liquid ahead of the planar solidification interface and describes macrosegregation has been developed. Two-phase dendritic and banded microstructures were grown in the Pb-Bi peritectic system, refined two-phase microstructures have were observed, and candidate formation mechanisms proposed. Material handling, containment, casting, microstructural and magnetic characterization techniques were developed for the Sm-Co system. Alloys produced with these procedures are homogeneous.

The growth of metastable peritectic compounds

NASA Technical Reports Server (NTRS)

Larson, D. J., Jr.

1984-01-01

The influence of gravitationally driven convection on the directional solidification of peritectic alloys was evaluated. The Pb-Bi peritectic was studied as a model solidification system. Analyses of directionally solidified Pb-Bi peritectic samples indicate that appreciable macrosegregation occurs due to thermosolutal convection and/or Soret diffusion. The macrosegregation results in sequantial change of phase and morphology as solidification progresses down the length of the sample. Banding was eliminated when furnace conditions were selected which resulted in a planar solidification interface. The directional solidification that occurs in the vicinity of the Pb-Bi peritectic isothermal was found to be isocompositional and to consist solely of the equilibrium terminal solid solution and peritectic phases on an extremely fine scale. Evidence was found to support the peritectic supercooling mechanism, but not the proposed peritectic superheat mechanism.

Heme compounds in dinosaur trabecular bone.

PubMed

Schweitzer, M H; Marshall, M; Carron, K; Bohle, D S; Busse, S C; Arnold, E V; Barnard, D; Horner, J R; Starkey, J R

1997-06-10

Six independent lines of evidence point to the existence of heme-containing compounds and/or hemoglobin breakdown products in extracts of trabecular tissues of the large theropod dinosaur Tyrannosaurus rex. These include signatures from nuclear magnetic resonance and electron spin resonance that indicate the presence of a paramagnetic compound consistent with heme. In addition, UV/visible spectroscopy and high performance liquid chromatography data are consistent with the Soret absorbance characteristic of this molecule. Resonance Raman profiles are also consistent with a modified heme structure. Finally, when dinosaurian tissues were extracted for protein fragments and were used to immunize rats, the resulting antisera reacted positively with purified avian and mammalian hemoglobins. The most parsimonious explanation of this evidence is the presence of blood-derived hemoglobin compounds preserved in the dinosaurian tissues.

The influence of precipitation kinetics on trace element partitioning between solid and liquid solutions: A coupled fluid dynamics/thermodynamics framework to predict distribution coefficients

NASA Astrophysics Data System (ADS)

Kavner, A.

2017-12-01

In a multicomponent multiphase geochemical system undergoing a chemical reaction such as precipitation and/or dissolution, the partitioning of species between phases is determined by a combination of thermodynamic properties and transport processes. The interpretation of the observed distribution of trace elements requires models integrating coupled chemistry and mechanical transport. Here, a framework is presented that predicts the kinetic effects on the distribution of species between two reacting phases. Based on a perturbation theory combining Navier-Stokes fluid flow and chemical reactivity, the framework predicts rate-dependent partition coefficients in a variety of different systems. We present the theoretical framework, with applications to two systems: 1. species- and isotope-dependent Soret diffusion of species in a multicomponent silicate melt subjected to a temperature gradient, and 2. Elemental partitioning and isotope fractionation during precipitation of a multicomponent solid from a multicomponent liquid phase. Predictions will be compared with results from experimental studies. The approach has applications for understanding chemical exchange in at boundary layers such as the Earth's surface magmatic systems and at the core/mantle boundary.

Anodic electrodeposition of NiTSPP from aqueous basic media.

PubMed

Pérez-Morales, Marta; Muñoz, Eulogia; Martín-Romero, María T; Camacho, Luis

2005-06-07

The oxidative electrodeposition of NiTSPP (tetrakis(4-sulfonatophenyl) Ni porphyrin) on ITO electrode from 0.1 M NaOH aqueous solution has been studied, and UV-visible and reflection FTIR spectroscopies have been used to analyze the composition of such film. By use of UV-vis spectroscopy, small absorbance of the film and an almost nulling effect on the Soret band of the porphyrin along the Ni(III)/Ni(II) redox process were observed. The reflection FTIR spectroscopy detected the presence of Ni-OH groups in the reduced film and as well the state of the porphyrin molecules as radical cation. Moreover, the porphyrin has been quantified by means of the area of the vibration bands assigned to the sulfonate groups by using as reference a Langmuir-Blodgett film containing a known surface concentration of NiTSPP. These results lead us propose the formation of a conductor salt by electrocrystallization, with stoichiometries TSPP/Ni(II)(OH)2 and TSPP/Ni(III)OOH, for its reduced and oxidized forms, respectively. In these two forms, the porphyrin rings will be present as radical cation, which may be stabilized through its dimerization or polymerization.

Highly luminescent, biocompatible ytterbium(iii) complexes as near-infrared fluorophores for living cell imaging.

PubMed

Ning, Yingying; Tang, Juan; Liu, Yi-Wei; Jing, Jing; Sun, Yuansheng; Zhang, Jun-Long

2018-04-21

Herein, we report the design and synthesis of biocompatible Yb 3+ complexes for near-infrared (NIR) living cell imaging. Upon excitation at either the visible (Soret band) or red region (Q band), these β-fluorinated Yb 3+ complexes display high NIR luminescence (quantum yields up to 23% and 13% in dimethyl sulfoxide and water, respectively) and have higher stabilities and prolonged decay lifetimes (up to 249 μs) compared to the β-non-fluorinated counterparts. This renders the β-fluorinated Yb 3+ complexes as a new class of biological optical probes in both steady-state imaging and time-resolved fluorescence lifetime imaging (FLIM). NIR confocal fluorescence images showed strong and specific intracellular Yb 3+ luminescence signals when the biocompatible Yb 3+ complexes were uptaken into the living cells. Importantly, FLIM measurements showed an intracellular lifetime distribution between 100 and 200 μs, allowing an effective discrimination from cell autofluorescence, and afforded high signal-to-noise ratios as firstly demonstrated in the NIR region. These results demonstrated the prospects of NIR lanthanide complexes as biological probes for NIR steady-state fluorescence and time-resolved fluorescence lifetime imaging.

Modeling of InP metalorganic chemical vapor deposition

NASA Technical Reports Server (NTRS)

Black, Linda R.; Clark, Ivan O.; Kui, J.; Jesser, William A.

1991-01-01

The growth of InP by metalorganic chemical vapor deposition (MOCVD) in a horizontal reactor is being modeled with a commercially available computational fluid dynamics modeling code. The mathematical treatment of the MOCVD process has four primary areas of concern: 1) transport phenomena, 2) chemistry, 3) boundary conditions, and 4) numerical solution methods. The transport processes involved in CVD are described by conservation of total mass, momentum, energy, and atomic species. Momentum conservation is described by a generalized form of the Navier-Stokes equation for a Newtonian fluid and laminar flow. The effect of Soret diffusion on the transport of particular chemical species and on the predicted deposition rate is examined. Both gas-phase and surface chemical reactions are employed in the model. Boundary conditions are specified at the inlet and walls of the reactor for temperature, fluid flow and chemical species. The coupled set of equations described above is solved by a finite difference method over a nonuniform rectilinear grid in both two and three dimensions. The results of the 2-D computational model is presented for gravity levels of zero- and one-g. The predicted growth rates at one-g are compared to measured growth rates on fused silica substrates.

Two-photon excited fluorescence emission from hemoglobin

NASA Astrophysics Data System (ADS)

Sun, Qiqi; Zeng, Yan; Zhang, Wei; Zheng, Wei; Luo, Yi; Qu, Jianan Y.

2015-03-01

Hemoglobin, one of the most important proteins in blood, is responsible for oxygen transportation in almost all vertebrates. Recently, we discovered two-photon excited hemoglobin fluorescence and achieved label-free microvascular imaging based on the hemoglobin fluorescence. However, the mechanism of its fluorescence emission still remains unknown. In this work, we studied the two-photon excited fluorescence properties of the hemoglobin subunits, heme/hemin (iron (II)/(III) protoporphyrin IX) and globin. We first studied the properties of heme and the similar spectral and temporal characteristics of heme and hemoglobin fluorescence provide strong evidence that heme is the fluorophore in hemoglobin. Then we studied the fluorescence properties of hemin, globin and methemoglobin, and found that the hemin may have the main effect on the methemoglobin fluorescence and that globin has tryptophan fluorescence like other proteins. Finally, since heme is a centrosymmetric molecule, that the Soret band fluorescence of heme and hemoglobin was not observed in the single photon process in the previous study may be due to the parity selection rule. The discovery of heme two-photon excited fluorescence may open a new window for heme biology research, since heme as a cofactor of hemoprotein has many functions, including chemical catalysis, electron transfer and diatomic gases transportation.

New porphyrins bearing positively charged peripheral groups linked by a sulfonamide group to meso-tetraphenylporphyrin: interactions with calf thymus DNA.

PubMed

Manono, Janet; Marzilli, Patricia A; Marzilli, Luigi G

2009-07-06

New water-soluble cationic meso-tetraarylporphyrins (TArP, Ar = 4-C(6)H(4)) and some metal derivatives have been synthesized and characterized. One main goal was to assess if N-methylpyridinium (N-Mepy) groups must be directly attached to the porphyrin core for intercalative binding of porphyrins to DNA. The new porphyrins have the general formula, [T(R(2)R(1)NSO(2)Ar)P]X(4/8) (R(1) = CH(3) or H and R(2) = N-Mepy-n-CH(2) with n = 2, 3, or 4; or R(1) = R(2) = Et(3)NCH(2)CH(2)). Interactions of selected porphyrins and metalloporphyrins (Cu(II), Zn(II)) with calf thymus DNA were investigated by visible circular dichroism (CD), absorption, and fluorescence spectroscopies. The DNA-induced changes in the porphyrin Soret region (a positive induced CD feature and, at high DNA concentration, increases in the Soret band and fluorescence intensities) indicate that the new porphyrins interact with DNA in an outside, non-self-stacking binding mode. Several new metalloporphyrins did not increase DNA solution viscosity and thus do not intercalate, confirming the conclusion drawn from spectroscopic studies. Porphyrins known to intercalate typically bear two or more N-Mepy groups directly attached to the porphyrin ring, such as the prototypical meso-tetra(N-Mepy)porphyrin tetracation (TMpyP(4)). The distances between the nitrogens of the N-Mepy group are estimated to be approximately 11 A (cis) and 16 A (trans) for the relatively rigid TMpyP(4). For the new flexible porphyrin, [T(N-Mepy-4-CH(2)(CH(3))NSO(2)Ar)P]Cl(4), the distances between the nitrogens are estimated to be able to span the range from approximately 9 to approximately 25 A. Thus, the N-Mepy groups in the new porphyrins can adopt the same spacing as in known intercalators such as TMpyP(4). The absence of intercalation by the new porphyrins indicates that the propensity for the N-Mepy group to facilitate DNA intercalation of cationic porphyrins requires direct attachment of N-Mepy groups to the porphyrin core.

Synthesis of chlorophyll-amino acid conjugates as models for modification of proteins with chromo/fluorophores.

PubMed

Tamiaki, Hitoshi; Isoda, Yasuaki; Tanaka, Takuya; Machida, Shinnosuke

2014-02-15

A chlorophyll-a derivative bonded directly with epoxide at the peripheral position of the chlorin π-system was reacted with N-urethane and C-ester protected amino acids bearing an alcoholic or phenolic hydroxy group as well as a carboxy group at the residue to give chlorophyll-amino acid conjugates. The carboxy residues of N,C-protected aspartic and glutamic acids were esterified with the epoxide in high yields. The synthetic conjugates in dichloromethane had absorption bands throughout the visible region including intense red-side Qy and blue-side Soret bands. By their excitation at the visible bands, strong and efficient fluorescence emission was observed up to the near-infrared region. The chromo/fluorophores are promising for preparation of functional peptides and modification of proteins. Copyright © 2013 Elsevier Ltd. All rights reserved.

Brown seaweed pigment as a dye source for photoelectrochemical solar cells

NASA Astrophysics Data System (ADS)

Calogero, Giuseppe; Citro, Ilaria; Di Marco, Gaetano; Armeli Minicante, Simona; Morabito, Marina; Genovese, Giuseppa

2014-01-01

Chlorophylls based-dyes obtained from seaweeds represent attractive alternatives to the expensive and polluting pyridil based Ru complexes because of their abundance in nature. Another important characteristic is that the algae do not subtract either cropland or agricultural water, therefore do not conflict with agro-food sector. This pigment shows a typical intense absorption in the UV/blue (Soret band) and a less intense band in the red/near IR (Q band) spectral regions and for these reasons appear very promising as sensitizer dyes for DSSC. In the present study, we utilized chlorophylls from samples of the brown alga Undaria pinnatifida as sensitizer in DSSCs. The dye, extracted by frozen seaweeds and used without any chemical purification, showed a very good fill factor (0.69). Even the photelectrochemical parameters if compared with the existent literature are very interesting.

A review: applications of the phase field method in predicting microstructure and property evolution of irradiated nuclear materials

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

Li, Yulan; Hu, Shenyang; Sun, Xin

Here, complex microstructure changes occur in nuclear fuel and structural materials due to the extreme environments of intense irradiation and high temperature. This paper evaluates the role of the phase field method in predicting the microstructure evolution of irradiated nuclear materials and the impact on their mechanical, thermal, and magnetic properties. The paper starts with an overview of the important physical mechanisms of defect evolution and the significant gaps in simulating microstructure evolution in irradiated nuclear materials. Then, the phase field method is introduced as a powerful and predictive tool and its applications to microstructure and property evolution in irradiatedmore » nuclear materials are reviewed. The review shows that (1) Phase field models can correctly describe important phenomena such as spatial-dependent generation, migration, and recombination of defects, radiation-induced dissolution, the Soret effect, strong interfacial energy anisotropy, and elastic interaction; (2) The phase field method can qualitatively and quantitatively simulate two-dimensional and three-dimensional microstructure evolution, including radiation-induced segregation, second phase nucleation, void migration, void and gas bubble superlattice formation, interstitial loop evolution, hydrate formation, and grain growth, and (3) The Phase field method correctly predicts the relationships between microstructures and properties. The final section is dedicated to a discussion of the strengths and limitations of the phase field method, as applied to irradiation effects in nuclear materials.« less

A review: applications of the phase field method in predicting microstructure and property evolution of irradiated nuclear materials

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

Li, Yulan; Hu, Shenyang; Sun, Xin

Complex microstructure changes occur in nuclear fuel and structural materials due to the extreme environments of intense irradiation and high temperature. This paper evaluates the role of the phase field (PF) method in predicting the microstructure evolution of irradiated nuclear materials and the impact on their mechanical, thermal, and magnetic properties. The paper starts with an overview of the important physical mechanisms of defect evolution and the significant gaps in simulating microstructure evolution in irradiated nuclear materials. Then, the PF method is introduced as a powerful and predictive tool and its applications to microstructure and property evolution in irradiated nuclearmore » materials are reviewed. The review shows that 1) FP models can correctly describe important phenomena such as spatial dependent generation, migration, and recombination of defects, radiation-induced dissolution, the Soret effect, strong interfacial energy anisotropy, and elastic interaction; 2) The PF method can qualitatively and quantitatively simulate 2-D and 3-D microstructure evolution, including radiation-induced segregation, second phase nucleation, void migration, void and gas bubble superlattice formation, interstitial loop evolution, hydrate formation, and grain growth, and 3) The FP method correctly predicts the relationships between microstructures and properties. The final section is dedicated to a discussion of the strengths and limitations of the PF method, as applied to irradiation effects in nuclear materials.« less

A review: applications of the phase field method in predicting microstructure and property evolution of irradiated nuclear materials

DOE PAGES

Li, Yulan; Hu, Shenyang; Sun, Xin; ...

2017-04-14

Here, complex microstructure changes occur in nuclear fuel and structural materials due to the extreme environments of intense irradiation and high temperature. This paper evaluates the role of the phase field method in predicting the microstructure evolution of irradiated nuclear materials and the impact on their mechanical, thermal, and magnetic properties. The paper starts with an overview of the important physical mechanisms of defect evolution and the significant gaps in simulating microstructure evolution in irradiated nuclear materials. Then, the phase field method is introduced as a powerful and predictive tool and its applications to microstructure and property evolution in irradiatedmore » nuclear materials are reviewed. The review shows that (1) Phase field models can correctly describe important phenomena such as spatial-dependent generation, migration, and recombination of defects, radiation-induced dissolution, the Soret effect, strong interfacial energy anisotropy, and elastic interaction; (2) The phase field method can qualitatively and quantitatively simulate two-dimensional and three-dimensional microstructure evolution, including radiation-induced segregation, second phase nucleation, void migration, void and gas bubble superlattice formation, interstitial loop evolution, hydrate formation, and grain growth, and (3) The Phase field method correctly predicts the relationships between microstructures and properties. The final section is dedicated to a discussion of the strengths and limitations of the phase field method, as applied to irradiation effects in nuclear materials.« less

Non-covalent interactions between thio-caffeine derivatives and water-soluble porphyrin in ethanol-water environment

NASA Astrophysics Data System (ADS)

Lipke, Agnieszka; Makarska-Bialokoz, Magdalena; Sierakowska, Arleta; Jasiewicz, Beata

2018-03-01

To determine the binding interactions and ability to form the non-covalent systems, the association process between 5,10,15,20-tetrakis[4-(trimethylammonio)phenyl]-21H,23H-porphine tetra-p-tosylate (H2TTMePP) and a series of five structurally diverse thio-caffeine analogues has been studied in ethanol and ethanol-water solutions, analyzing its absorption and steady-state fluorescence spectra. The porphyrin fluorescence lifetimes in the systems studied were established as well. During the titration with thio-caffeine compounds the slight bathochromic effect and considerable hypochromicity of the porphyrin Soret band maximum can be noted. The fluorescence quenching effect observed for interactions in H2TTMePP - thio-caffeine derivative systems, as well as the order of binding and fluorescence quenching constants (of 105-103 mol- 1) suggest the existence of the mechanism of static quenching due to the formation of non-covalent and non-fluorescent stacking complexes. In all the systems studied the phenomenon of the fractional accessibility of the fluorophore for the quencher was observed as well. Additionally, the specific binding interactions, due to the changes in reaction environment polarity, can be observed. It was found that thio-caffeine compounds can quench the porphyrin fluorescence according to the structure of thio-substituent in caffeine molecule. The obtained results can be potentially useful from scientific, therapeutic or environmental points of view.

Lattice-Boltzmann-based simulations of diffusiophoresis of colloids and cells

NASA Astrophysics Data System (ADS)

Kreft Pearce, Jennifer; Castigliego, Joshua

Increasing environmental degradation due to plastic pollutants requires innovative solutions that facilitate the extraction of pollutants without harming local biota. We present results from a lattice-Boltzmann-base Brownian Dynamics simulation on diffusiophoresis and the separation of particles within the system. A gradient in viscosity that simulates a concentration gradient in a dissolved polymer allows us to separate various types of particles based on their deformability. As seen in previous experiments, simulated particles that have a higher deformability react differently to the polymer matrix than those with a lower deformability. Therefore, the particles can be separated from each other. The system described above was simulated with various concentration gradients as well as various Soret coefficients in order to optimize the separation of the particles. This simulation, in particular, was intended to model an oceanic system where the particles of interest were motile and nonmotile plankton and microplastics. The separation of plankton from the microplastics was achieved.

Desferrioxamine as an electron donor. Inhibition of membranal lipid peroxidation initiated by H2O2-activated metmyoglobin and other peroxidizing systems.

PubMed

Kanner, J; Harel, S

1987-01-01

Desferrioxamine (DFO) involvement in several peroxidative systems was studied. These systems included: a) membranal lipid peroxidation initiated by H2O2-activated metmyoglobin (or methemoglobin); b) phenol-red oxidation by activated metmyoglobin or horseradish peroxidase (HRP): c) beta-carotene-linoleate couple oxidation stimulated by lipoxygenase or hemin. Desferrioxamine was found to inhibit all these systems but not ferrioxamine (FO). Phenol-red oxidation by H2O2-horseradish peroxidase was inhibited competitively with DFO. Kinetic studies using the spectra changes in the Soret region of metmyoglobin suggest a mechanism by which H2O2 reacts with the iron-heme to form an intermediate of oxy-ferryl myoglobin that subsequently reacts with DFO to return the activated compound to the resting state. These activities of DFO resemble the reaction of other electron donors.

Insert Concepts for the Material Science Research Rack (MSRR-1) of the Material Science Research Facility (MSRF) on the International Space Station (ISS)

NASA Technical Reports Server (NTRS)

Crouch, Myscha; Carswell, Bill; Farmer, Jeff; Rose, Fred; Tidwell, Paul

2000-01-01

The Material Science Research Rack I (MSRR-1) of the Material Science Research Facility (MSRF) contains an Experiment Module (EM) being developed collaboratively by NASA and the European Space Agency (ESA). This NASA/ESA EM will accommodate several different removable and replaceable Module Inserts (MIs) which are installed on orbit NASA's planned inserts include the Quench Module Insert (QMI) and the Diffusion Module Insert (DMI). The QMI is a high-gradient Bridgman-type vacuum furnace with quench capabilities used for experiments on directional solidification of metal alloys. The DMI is a vacuum Bridgman-Stockbarger-type furnace for experiments on Fickian and Soret diffusion in liquids. This paper discusses specific design features and performance capabilities of each insert. The paper also presents current prototype QMI hardware analysis and testing activities and selected results.

Purification and partial characterization of haloperoxidase from fresh water algae Cladophora glomerata.

PubMed

Verdel, E F; Kline, P C; Wani, S; Woods, A E

2000-02-01

Many haloperoxidases have been purified from diverse organisms, including lichen, fungi, bacteria, and marine algae. In this study a haloperoxidase was purified from the fresh water algae, Cladophora glomerata, by homogenization and centrifugation, ammonium sulfate fractionation, ion-exchange and gel filtration chromatography. Molecular weight was determined by SDS-PAGE and by size exclusion HPLC and found to be approximately 43 kDa. The isoelectric point was determined to be approximately 8.1 by isoelectric focusing. The UV spectrum of the peroxidase showed a strong absorbance in the Soret band indicating a heme protein, unlike vanadium-dependent haloperoxidases from marine algae. Fresh water algal haloperoxidase catalyzed the iodination of tyrosine at a pH of 3.1. This haloperoxidase also catalyzes the oxidation of guaiacol and oxidation of iodide as well as catalyzing a peroxide-dependent reaction in both the presence and absence of chloride and bromide ions.

Control strategy on the double-diffusive convection in a nanofluid layer with internal heat generation

NASA Astrophysics Data System (ADS)

Mokhtar, N. F. M.; Khalid, I. K.; Siri, Z.; Ibrahim, Z. B.; Gani, S. S. A.

2017-10-01

The influences of feedback control and internal heat source on the onset of Rayleigh-Bénard convection in a horizontal nanofluid layer is studied analytically due to Soret and Dufour parameters. The confining boundaries of the nanofluid layer (bottom boundary-top boundary) are assumed to be free-free, rigid-free, and rigid-rigid, with a source of heat from below. Linear stability theory is applied, and the eigenvalue solution is obtained numerically using the Galerkin technique. Focusing on the stationary convection, it is shown that there is a positive thermal resistance in the presence of feedback control on the onset of double-diffusive convection, while there is a positive thermal efficiency in the existence of internal heat generation. The possibilities of suppress or augment of the Rayleigh-Bénard convection in a nanofluid layer are also discussed in detail.

Steady boundary layer slip flow along with heat and mass transfer over a flat porous plate embedded in a porous medium.

PubMed

Aziz, Asim; Siddique, J I; Aziz, Taha

2014-01-01

In this paper, a simplified model of an incompressible fluid flow along with heat and mass transfer past a porous flat plate embedded in a Darcy type porous medium is investigated. The velocity, thermal and mass slip conditions are utilized that has not been discussed in the literature before. The similarity transformations are used to transform the governing partial differential equations (PDEs) into a nonlinear ordinary differential equations (ODEs). The resulting system of ODEs is then reduced to a system of first order differential equations which was solved numerically by using Matlab bvp4c code. The effects of permeability, suction/injection parameter, velocity parameter and slip parameter on the structure of velocity, temperature and mass transfer rates are examined with the aid of several graphs. Moreover, observations based on Schmidt number and Soret number are also presented. The result shows, the increase in permeability of the porous medium increase the velocity and decrease the temperature profile. This happens due to a decrease in drag of the fluid flow. In the case of heat transfer, the increase in permeability and slip parameter causes an increase in heat transfer. However for the case of increase in thermal slip parameter there is a decrease in heat transfer. An increase in the mass slip parameter causes a decrease in the concentration field. The suction and injection parameter has similar effect on concentration profile as for the case of velocity profile.

Steady Boundary Layer Slip Flow along with Heat and Mass Transfer over a Flat Porous Plate Embedded in a Porous Medium

PubMed Central

Aziz, Asim; Siddique, J. I.; Aziz, Taha

2014-01-01

In this paper, a simplified model of an incompressible fluid flow along with heat and mass transfer past a porous flat plate embedded in a Darcy type porous medium is investigated. The velocity, thermal and mass slip conditions are utilized that has not been discussed in the literature before. The similarity transformations are used to transform the governing partial differential equations (PDEs) into a nonlinear ordinary differential equations (ODEs). The resulting system of ODEs is then reduced to a system of first order differential equations which was solved numerically by using Matlab bvp4c code. The effects of permeability, suction/injection parameter, velocity parameter and slip parameter on the structure of velocity, temperature and mass transfer rates are examined with the aid of several graphs. Moreover, observations based on Schmidt number and Soret number are also presented. The result shows, the increase in permeability of the porous medium increase the velocity and decrease the temperature profile. This happens due to a decrease in drag of the fluid flow. In the case of heat transfer, the increase in permeability and slip parameter causes an increase in heat transfer. However for the case of increase in thermal slip parameter there is a decrease in heat transfer. An increase in the mass slip parameter causes a decrease in the concentration field. The suction and injection parameter has similar effect on concentration profile as for the case of velocity profile. PMID:25531301

Structure and physicochemical properties of thin film photosemiconductor cells based on porphine derivatives

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

Kazak, A. V., E-mail: alexkazak86@gmail.com; Usol’tseva, N. V.; Smirnova, A. I.

2016-05-15

Photosemiconductor thin films based on two organic porphine derivatives have been investigated. These compounds have different pendent groups; the film morphology, along with the specific fabrication technique, is determined to a great extent by these groups. The films have been fabricated by vacuum sputtering and using the Langmuir−Schaefer method. According to the atomic force microscopy (AFM) data, the Langmuir−Schaefer films are more homogeneous than the sputtered ones. It is shown that the sputtered films based on substituted porphine have a looser stacking than the initial analog. A spectroscopy study revealed a bathochromic shift of the Soret band in the Langmuir−Schaefermore » films–sputtered films series. This shift is explained by the increase in the concentration and size of molecular aggregates in sputtered films. It is shown that a polycrystalline C{sub 60} fullerene film deposited onto an amorphous substituted porphine layer improves the photoelectric characteristics of the latter. Both the time stability of the photodiode structure and its ampere‒watt sensitivity increase (by a factor of 10 in the transition regime). The steady-state current does not change. The effect of polarity reversal of the photovoltaic signal is observed in a planar C{sub 60}‒substituted metalloporphine heterostructure, which is similar to the pyroelectric effect. The polarity reversal can be explained by the contribution of the trap charge and discharge current at the interface between the amorphous photosemiconductor and crystalline photosemiconductor to the resulting photoelectric current.« less

The origin of Karaj dam basement sill marginal reversal by Soret fractionation

NASA Astrophysics Data System (ADS)

Maghdour-Mashhour, Reza; Esmaeily, Dariush

2010-05-01

The Karaj dam basement sill (KDBS), located North West of Tehran, northern Iran, is one of the several E-W-trending plutons in the Albourz Mountains. The KDBS consists of a layered series between upper and lower chilled margins. The rocks of the chilled margins are gabbroic in composition and porphyritic, with euhedral to subhedral plagioclase and clinopyroxene megacrysts up to 5 mm long. The rocks become coarse-grained toward the center of the sill and show a gradual transition from porphyritic to equigranular texture. Field and petrographic observations reveal a reverse trend in marginal units crystallization from the eutectic point to the main magma composition; i.e., the olivine-bearing gabbro (porphyritic chilled margin), which has a eutectic composition, crystallized prior to the marginal gabbros, which have a cotectic or near-cotectic composition, as plagioclase laths in the gabbroic unit are embedded in large crystals of clinopyroxene and this phenomenon is believed to result from the cotectic crystallization of plagioclase and clinopyroxene. Four major mechanisms are proposed and discussed in order to find the exact mechanism responsible for marginal reversal formation as following: 1) Crystal settling is a gravity-dependent mechanism and phenocrysts must have settled to form a layer at the bottom of the sill, showing sharp upper boundary which is not observable in KDBS. Besides, the reverse fractionation of inwardly-dipping sequence of mentioned sill occurs in layers with primary dips up to 55°. Consequently capability of marginal reversals to develop along steeply inclined chamber margins, by this mechanism is implausible. 2) Multiple injections of successive magma pulses fails to explain the origin of marginal reversal since the transition along the entire length of marginal reversal is gradual also there is no compositional break or chilled contact between two mentioned units of KDBS margin (Olivine-gabbro and marginal gabbro). 3) The idea of supercooling could not be applied to the marginal series as well. Because the high degree of supercooling would make the marginal series with a fine-grained chilled margins which is far from being observed in KDBS. 4) Soret fractionation is the most probable mechanism among the others which has recently taken into account by researchers (e.g. Latypov, 2003). As shown by Worster et al. (1990), vigorous convection can be logically assumed to be a major process responsible for the generation of smooth trends in the distribution of cumulate minerals in the accumulation zone and the gradual transition between different layers, which are characteristic features of the KDBS confirm the occurrence of vigorous convection in the main magma reservoir. Vigorous magma convection in the KDBS chamber leads to the formation of a thin thermal boundary layer along the chamber margins, thereby maintaining the temperature contrast from fading and ensuring the continuous exchange of HMPCs (e.g., MgO) across the liquid boundary layer from the margins toward the main magma chamber and for LMPCs in opposite direction, by Soret diffusion. Consequently further decrease in the magnitude of the thermal gradient within the boundary layer would have caused a gradual change in the composition of the liquids in the boundary layer, becoming progressively depleted in LMPCs, shifting away from the eutectic point Ol + Pl + Cpx + L along the cotectic line Cpx + Pl + L. In this way, crystallization of the developing cumulus front in the liquid boundary layer produced the compositional sequence in reverse order, from the eutectic point to the initial parental magma, resulting in the occurrence of olivine-bearing gabbro in the chilled margins and gabbros toward the center of chamber.

Tetrabutylammonium Salts of Aluminum(III) and Gallium(III) Phthalocyanine Radical Anions Bonded with Fluoren-9-olato- Anions and Indium(III) Phthalocyanine Bromide Radical Anions.

PubMed

Konarev, Dmitri V; Khasanov, Salavat S; Ishikawa, Manabu; Nakano, Yoshiaki; Otsuka, Akihiro; Yamochi, Hideki; Saito, Gunzi; Lyubovskaya, Rimma N

2017-04-18

Reduction of aluminum(III), gallium(III), and indium(III) phthalocyanine chlorides by sodium fluorenone ketyl in the presence of tetrabutylammonium cations yielded crystalline salts of the type (Bu 4 N + ) 2 [M III (HFl-O - )(Pc .3- )] .- (Br - )⋅1.5 C 6 H 4 Cl 2 [M=Al (1), Ga (2); HFl-O - =fluoren-9-olato - anion; Pc=phthalocyanine] and (Bu 4 N + ) [In III Br(Pc .3- )] .- ⋅0.875 C 6 H 4 Cl 2 ⋅0.125 C 6 H 14 (3). The salts were found to contain Pc .3- radical anions with negatively charged phthalocyanine macrocycles, as evidenced by the presence of intense bands of Pc .3- in the near-IR region and a noticeable blueshift in both the Q and Soret bands of phthalocyanine. The metal(III) atoms coordinate HFl-O - anions in 1 and 2 with short Al-O and Ga-O bond lengths of 1.749(2) and 1.836(6) Å, respectively. The C-O bonds [1.402(3) and 1.391(11) Å in 1 and 2, respectively] in the HFl-O - anions are longer than the same bond in the fluorenone ketyl (1.27-1.31 Å). Salts 1-3 show effective magnetic moments of 1.72, 1.66, and 1.79 μ B at 300 K, respectively, owing to the presence of unpaired S=1/2 spins on Pc .3- . These spins are coupled antiferromagnetically with Weiss temperatures of -22, -14, and -30 K for 1-3, respectively. Coupling can occur in the corrugated two-dimensional phthalocyanine layers of 1 and 2 with an exchange interaction of J/k B =-0.9 and -1.1 K, respectively, and in the π-stacking {[In III Br(Pc .3- )] .- } 2 dimers of 3 with an exchange interaction of J/k B =-10.8 K. The salts show intense electron paramagnetic resonance (EPR) signals attributed to Pc .3- . It was found that increasing the size of the central metal atom strongly broadened these EPR signals. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Latex Clearing Protein (Lcp) of Streptomyces sp. Strain K30 Is a b-Type Cytochrome and Differs from Rubber Oxygenase A (RoxA) in Its Biophysical Properties

PubMed Central

Birke, Jakob; Röther, Wolf

2015-01-01

Specific polyisoprene-cleaving activities of 1.5 U/mg and 4.6 U/mg were determined for purified Strep-tagged latex clearing protein (Lcp) of Streptomyces sp. strain K30 at 23°C and 37°C, respectively. Metal analysis revealed the presence of approximately one atom of iron per Lcp molecule. Copper, which had been identified in Lcp1VH2 of Gordonia polyisoprenivorans previously, was below the detection limit in LcpK30. Heme was identified as a cofactor in purified LcpK30 by (i) detection of characteristic α-, β-, and γ (Soret)-bands at 562 nm, 532 nm, and 430 nm in the visible spectrum after chemical reduction, (ii) detection of an acetone-extractable porphyrin molecule, (iii) determination of a heme b-type-specific absorption maximum (556 nm) after chemical conversion of the heme group to a bipyridyl-heme complex, and (iv) detection of a b-heme-specific m/z value of 616.2 via mass spectrometry. Spectroscopic analysis showed that purified Lcp as isolated contains an oxidized heme-Fe3+ that is free of bound dioxygen. This is in contrast to the rubber oxygenase RoxA, a c-type heme-containing polyisoprene-cleaving enzyme present in Gram-negative rubber degraders, in which the covalently bound heme firmly binds a dioxygen molecule. LcpK30 also differed from RoxA in the lengths of the rubber degradation cleavage products and in having a higher melting point of 61.5°C (RoxA, 54.3°C). In summary, RoxA and Lcp both are equipped with a heme cofactor and catalyze an oxidative C-C cleavage reaction but differ in the heme subgroup type and in several biochemical and biophysical properties. These findings suggest differences in the catalytic reaction mechanisms. PMID:25819959

The non-contact detection and identification of blood stained fingerprints using visible wavelength hyperspectral imaging: Part II effectiveness on a range of substrates.

PubMed

Cadd, Samuel; Li, Bo; Beveridge, Peter; O'Hare, William T; Campbell, Andrew; Islam, Meez

2016-05-01

Biological samples, such as blood, are regularly encountered at violent crime scenes and successful identification is critical for criminal investigations. Blood is one of the most commonly encountered fingerprint contaminants and current identification methods involve presumptive tests or wet chemical enhancement. These are destructive however; can affect subsequent DNA sampling; and do not confirm the presence of blood, meaning they are susceptible to false positives. A novel application of visible wavelength reflectance hyperspectral imaging (HSI) has been used for the non-contact, non-destructive detection and identification of blood stained fingerprints across a range of coloured substrates of varying porosities. The identification of blood was based on the Soret γ band absorption of haemoglobin between 400 nm and 500 nm. Ridge detail was successfully visualised to the third depletion across light coloured substrates and the stain detected to the tenth depletion on both porous and non-porous substrates. A higher resolution setup for blood stained fingerprints on black tiles, detected ridge detail to the third depletion and the stain to the tenth depletion, demonstrating considerable advancements from previous work. Diluted blood stains at 1500 and 1000 fold dilutions for wet and dry stains respectively were also detected on pig skin as a replica for human skin. Copyright © 2016 The Chartered Society of Forensic Sciences. Published by Elsevier Ireland Ltd. All rights reserved.

Temperature-gradient-induced

NASA Astrophysics Data System (ADS)

Park, Cheol; Glaser, Matt; Maclennan, Joe; Clark, Noel; Trittel, Torsten; Stannarius, Ralf

Freely-suspended smectic films of sub-micrometer thickness and lateral extensions of several millimeters were used to study thermally driven migration and convection in the film plane. Film experiments were performed during the 6 minute microgravity phase of a TEXUS suborbital rocket flight (Texus 52, launched April 27, 2015). We have found an attraction of the smectic material towards the cold edge of the film in a temperature gradient, similar to the Soret effect. This process is reversed when this edge is heated up again. Thermal convection driven by two thermocontacts in the film is practically absent, even at temperature gradients up to 10 K/mm, with thermally driven convection only setting in when the hot post reaches the transition temperature to the nematic phase. The Observation and Analysis of Smectic Islands in Space (OASIS) flight hardware was launched on SpaceX-6 in April 2015 and experiments on smectic bubbles were carried out on the International Space Station using four different smectic A and C liquid crystal materials in separate sample chambers. We observed that smectic islands on the surface of the bubbles migrated towards the colder part of the bubble in a temperature gradient. This work was supported by NASA Grant No. NNX-13AQ81G, by the Soft Materials Research Center under NSF MRSEC Grants No. DMR-0820579 and No. DMR-1420736, and by DLR Grants 50WM1127 and 50WM1430.

Estimation of the tritium retention in ITER tungsten divertor target using macroscopic rate equations simulations

NASA Astrophysics Data System (ADS)

Hodille, E. A.; Bernard, E.; Markelj, S.; Mougenot, J.; Becquart, C. S.; Bisson, R.; Grisolia, C.

2017-12-01

Based on macroscopic rate equation simulations of tritium migration in an actively cooled tungsten (W) plasma facing component (PFC) using the code MHIMS (migration of hydrogen isotopes in metals), an estimation has been made of the tritium retention in ITER W divertor target during a non-uniform exponential distribution of particle fluxes. Two grades of materials are considered to be exposed to tritium ions: an undamaged W and a damaged W exposed to fast fusion neutrons. Due to strong temperature gradient in the PFC, Soret effect’s impacts on tritium retention is also evaluated for both cases. Thanks to the simulation, the evolutions of the tritium retention and the tritium migration depth are obtained as a function of the implanted flux and the number of cycles. From these evolutions, extrapolation laws are built to estimate the number of cycles needed for tritium to permeate from the implantation zone to the cooled surface and to quantify the corresponding retention of tritium throughout the W PFC.

Ultrafast Relaxation Dynamics of Photoexcited Zinc-Porphyrin: Electronic-Vibrational Coupling

DOE PAGES

Abraham, Baxter; Nieto-Pescador, Jesus; Gundlach, Lars

2016-08-02

Cyclic tetrapyrroles are the active core of compounds with crucial roles in living systems, such as hemoglobin and chlorophyll, and in technology as photocatalysts and light absorbers for solar energy conversion. Zinc-tetraphenylporphyrin (Zn-TPP) is a prototypical cyclic tetrapyrrole that has been intensely studied in past decades. Because of its importance for photochemical processes the optical properties are of particular interest, and, accordingly, numerous studies have focused on light absorption and excited-state dynamics of Zn-TPP. Relaxation after photoexcitation in the Soret band involves internal conversion that is preceded by an ultrafast process. This relaxation process has been observed by several groups.more » Until now, it has not been established if it involves a higher lying ”dark” state or vibrational relaxation in the excited S 2 state. Here we combine high time resolution electronic and vibrational spectroscopy to show that this process constitutes vibrational relaxation in the anharmonic 2 potential.« less

Ultrafast Relaxation Dynamics of Photoexcited Zinc-Porphyrin: Electronic-Vibrational Coupling

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

Abraham, Baxter; Nieto-Pescador, Jesus; Gundlach, Lars

Cyclic tetrapyrroles are the active core of compounds with crucial roles in living systems, such as hemoglobin and chlorophyll, and in technology as photocatalysts and light absorbers for solar energy conversion. Zinc-tetraphenylporphyrin (Zn-TPP) is a prototypical cyclic tetrapyrrole that has been intensely studied in past decades. Because of its importance for photochemical processes the optical properties are of particular interest, and, accordingly, numerous studies have focused on light absorption and excited-state dynamics of Zn-TPP. Relaxation after photoexcitation in the Soret band involves internal conversion that is preceded by an ultrafast process. This relaxation process has been observed by several groups.more » Until now, it has not been established if it involves a higher lying ”dark” state or vibrational relaxation in the excited S 2 state. Here we combine high time resolution electronic and vibrational spectroscopy to show that this process constitutes vibrational relaxation in the anharmonic 2 potential.« less

Electronic resonances in broadband stimulated Raman spectroscopy

NASA Astrophysics Data System (ADS)

Batignani, G.; Pontecorvo, E.; Giovannetti, G.; Ferrante, C.; Fumero, G.; Scopigno, T.

2016-01-01

Spontaneous Raman spectroscopy is a formidable tool to probe molecular vibrations. Under electronic resonance conditions, the cross section can be selectively enhanced enabling structural sensitivity to specific chromophores and reaction centers. The addition of an ultrashort, broadband femtosecond pulse to the excitation field allows for coherent stimulation of diverse molecular vibrations. Within such a scheme, vibrational spectra are engraved onto a highly directional field, and can be heterodyne detected overwhelming fluorescence and other incoherent signals. At variance with spontaneous resonance Raman, however, interpreting the spectral information is not straightforward, due to the manifold of field interactions concurring to the third order nonlinear response. Taking as an example vibrational spectra of heme proteins excited in the Soret band, we introduce a general approach to extract the stimulated Raman excitation profiles from complex spectral lineshapes. Specifically, by a quantum treatment of the matter through density matrix description of the third order nonlinear polarization, we identify the contributions which generate the Raman bands, by taking into account for the cross section of each process.

Kinetics and equilibria of cyanide binding to prostaglandin H synthase.

PubMed

MacDonald, I D; Dunford, H B

1989-09-01

Cyanide binding to prostaglandin H (PGH) synthase results in a spectral shift in the Soret region. This shift was exploited to determine equilibrium and kinetic parameters of the cyanide binding process. At pH 8.0, ionic strength 0.22 M, 4 degrees C, the cyanide dissociation constant, determined from equilibrium experiments, is (65 +/- 10) microM. The binding rate constant is (2.8 +/- 0.2) x 10(3) M-1 s-1, and the dissociation rate constant is zero within experimental error. Through a kinetic study of the binding process as a function of pH, from pH 3.96 to 8.00, it was possible to determine the pKa of a heme-linked acid group on the enzyme of 4.15 +/- 0.10 with citrate buffer. An apparent pKa of 4.75 +/- 0.03 was determined with acetate buffer; this different value is attributed to complexation of the enzyme with one of the components of the acetate buffer.

Clay induced aggregation of a tetra-cationic metalloporphyrin in Layer by Layer self assembled film

NASA Astrophysics Data System (ADS)

Banik, Soma; Bhattacharjee, J.; Hussain, S. A.; Bhattacharjee, D.

2015-12-01

Porphyrins have a general tendency to form aggregates in ultrathin films. Also electrostatic adsorption of cationic porphyrins onto anionic nano clay platelets results in the flattening of porphyrin moieties. The flattening is evidenced by the red-shifting of Soret band with respect to the aqueous solution. In the present communication, we have studied the clay induced aggregation behaviour of a tetra-cationic metalloporphyrin Manganese (III) 5, 10, 15, 20-tetra (4 pyridyl)-21 H, 23 H-porphine chloride tetrakis (methochloride) (MnTMPyP) in Layer-by-Layer (LbL) self assembled film. The adsorption of dye molecules onto nano clay platelets resulted in the flattening of the meso substituent groups of the dye chromophore. In Layer-by-Layer ultrathin film, the flattened porphyrin molecules tagged nano clay platelets were further associated to form porphyrin aggregates. This has been clearly demonstrated from the UV-vis absorption spectroscopic studies. Atomic Force Microscopic (AFM) studies gave visual evidence of the association of organo-clay hybrid molecules in the LbL film.

Electroactive Film of Myoglobin Incorporated in a 3D-porous Calcium Alginate Film with Polyvinyl Alcohol, Glycerin and Gelatin.

PubMed

Zheng, Xueqin; Sun, Hong; Hou, Shifeng

2015-01-01

In this work, an electroactive porous Mb-CA's composite film was fabricated by incorporating myoglobin (Mb) in a three-dimension (3D) porous calcium alginate (CA) film with polyvinyl alcohol, glycerol, and gelatin. The porous Mb-CA's film modified electrodes exhibited a pair of well-defined, quasi-reversible cyclic voltammetric (CV) peaks at about -0.37 V vs. SCE in pH 7.0 buffers, characteristic of Mb heme Fe((III))/Fe((II)) redox couples. The electrochemical parameters, such as formal potentials (E(o')) and apparent heterogeneous electron-transfer rate constants (ks), were estimated by square-wave voltammetry with nonlinear regression analysis. The porous CA's composite film could form hydrogel in aqueous solution. The positions of the Soret absorbance band suggest that Mb in the CA's composite film kept its native states in the medium pH range. Hydrogen peroxide, oxygen, and nitrite were electrochemically catalyzed by the Mb-CA's composite film with significant lowering of the reduction overpotential.

Synthesis of Tumor-avid Photosensitizer-Gd(III)DTPA conjugates: impact of the number of gadolinium units in T1/T2 relaxivity, intracellular localization, and photosensitizing efficacy.

PubMed

Goswami, Lalit N; White, William H; Spernyak, Joseph A; Ethirajan, Manivannan; Chen, Yihui; Missert, Joseph R; Morgan, Janet; Mazurchuk, Richard; Pandey, Ravindra K

2010-05-19

To develop novel bifunctional agents for tumor imaging (MR) and photodynamic therapy (PDT), certain tumor-avid photosensitizers derived from chlorophyll-a were conjugated with variable number of Gd(III)aminobenzyl DTPA moieties. All the conjugates containing three or six gadolinium units showed significant T(1) and T(2) relaxivities. However, as a bifunctional agent, the 3-(1'-hexyloxyethyl)pyropheophorbide-a (HPPH) containing 3Gd(III) aminophenyl DTPA was most promising with possible applications in tumor-imaging and PDT. Compared to HPPH, the corresponding 3- and 6Gd(III)aminobenzyl DTPA conjugates exhibited similar electronic absorption characteristics with a slightly decreased intensity of the absorption band at 660 nm. However, compared to HPPH, the excitation of the broad "Soret" band (near 400 nm) of the corresponding 3Gd(III)aminobenzyl-DTPA analogues showed a significant decrease in the fluorescence intensity at 667 nm.

Synthesis, characterization and photophysical properties of ferrocenyl and mixed sandwich cobaltocenyl ester linked meso-triaryl corrole dyads

NASA Astrophysics Data System (ADS)

Achary, B. Shivaprasad; Ramya, A. R.; Trivedi, Rajiv; Bangal, P. R.; Giribabu, L.

We report here the design and synthesis of corrole-metallocene dyads consisting of a metallocene (either ferrocene (Dyad 1) or mixed sandwich η5-[C5H4(COOH)]Co(η4-C4Ph4) (Dyad 2)) connected via an ester linkage at meso phenyl position. Both the dyads were characterized by 1H NMR, MALDI-TOF, UV-visible, fluorescence spectroscopies (steady-state, picosecond time-resolved), femtosecond transient absorption spectroscopy (fs-TA) and electrochemical methods. The absorption spectra of these dyads showed slight broadening and splitting of the Soret band that indicates a weak ground state interaction between the corrole macrocycle and metallocene part of the present donor-acceptor (D-A) system. However, in both the dyad systems, fluorescence emission of the corrole was quenched in polar solvents as compared to its parent compound 10-(4-hydroxyphenyl)-5,15-bis-(pentafluorophenyl ) corrole (Ph-Corr). The quenching was more pronounced in ferrocene derivatives than in cobaltocenyl derivatives. Transient absorption studies confirm the absence of photoinduced electron transfer from metallocene to correl for these dyad systems and the quenching of singlet state of corrole is found to enhance intersystem crossing due to heavy atom effect. Corrole-ferrocene and corrole-mixed sandwich η5-[C5H4(COOH)]Co(η4-C4Ph4) dyads have been designed, synthesized and characterized by various spectroscopic techniques. Emission intensitiy of both dyads were quenched in polar solvents whereas transient absorption studies indicates that the quenching coule be due to the heavy atom effect.

Changes in the Martian atmosphere induced by auroral electron precipitation

NASA Astrophysics Data System (ADS)

Shematovich, V. I.; Bisikalo, D. V.; Gérard, J.-C.; Hubert, B.

2017-09-01

Typical auroral events in the Martian atmosphere, such as discrete and diffuse auroral emissions detected by UV spectrometers onboard ESA Mars Express and NASA MAVEN, are investigated. Auroral electron kinetic energy distribution functions and energy spectra of the upward and downward electron fluxes are obtained by electron transport calculations using the kinetic Monte Carlo model. These characteristics of auroral electron fluxes make it possible to calculate both the precipitation-induced changes in the atmosphere and the observed manifestations of auroral events on Mars. In particular, intensities of discrete and diffuse auroral emissions in the UV and visible wavelength ranges (Soret et al., 2016; Bisikalo et al., 2017; Gérard et al., 2017). For these conditions of auroral events, the analysis is carried out, and the contribution of the fluxes of precipitating electrons to the heating and ionization of the Martian atmosphere is estimated. Numerical calculations show that in the case of discrete auroral events the effect of the residual crustal magnetic field leads to a significant increase in the upward fluxes of electrons, which causes a decrease in the rates of heating and ionization of the atmospheric gas in comparison with the calculations without taking into account the residual magnetic field. It is shown that all the above-mentioned impact factors of auroral electron precipitation processes should be taken into account both in the photochemical models of the Martian atmosphere and in the interpretation of observations of the chemical composition and its variations using the ACS instrument onboard ExoMars.

Stability of the heme environment of the nitric oxide synthase from Staphylococcus aureus in the absence of pterin cofactor.

PubMed

Chartier, François J M; Couture, Manon

2004-09-01

We have used resonance Raman spectroscopy to probe the heme environment of a recently discovered NOS from the pathogenic bacterium Staphylococcus aureus, named SANOS. We detect two forms of the CO complex in the absence of L-arginine, with nu(Fe-CO) at 482 and 497 cm(-1) and nu(C-O) at 1949 and 1930 cm(-1), respectively. Similarly to mammalian NOS, the binding of L-arginine to SANOS caused the formation of a single CO complex with nu(Fe-CO) and nu(C-O) frequencies at 504 and 1,917 cm(-1), respectively, indicating that L-arginine induced an electrostatic/steric effect on the CO molecule. The addition of pterins to CO-bound SANOS modified the resonance Raman spectra only when they were added in combination with L-arginine. We found that (6R) 5,6,7,8 tetra-hydro-L-biopterin and tetrahydrofolate were not required for the stability of the reduced protein, which is 5-coordinate, and of the CO complex, which does not change with time to a form with a Soret band at 420 nm that is indicative of a change of the heme proximal coordination. Since SANOS is stable in the absence of added pterin, it suggests that the role of the pterin cofactor in the bacterial NOS may be limited to electron/proton transfer required for catalysis and may not involve maintaining the structural integrity of the protein as is the case for mammalian NOS.

Dis-aggregation of an insoluble porphyrin in a calixarene matrix: characterization of aggregate modes by extended dipole model.

PubMed

de Miguel, Gustavo; Martín-Romero, María T; Pedrosa, José M; Muñoz, Eulogia; Pérez-Morales, Marta; Richardson, Tim H; Camacho, Luis

2008-03-21

In this paper, the different aggregation modes of a water-insoluble porphyrin (EHO) mixed with an amphiphilic calix[8]arene (C8A), at the air-water interface and in Langmuir-Blodgett (LB) film form, are analyzed as a function of the mixed composition. The strategy used to control the EHO aggregation has consisted of preparing mixed thin films containing EHO and C8A, in different ratios, at the air-water interface. Therefore, the increase of the C8A molar ratio in the mixed film diminishes the aggregation of the EHO molecules, although such an effect must be exclusively related to the dilution of the porphyrin. The reflection spectra of the mixed C8A-EHO films registered at the air-water interface, show a complex Soret band exhibiting splitting, hypochromicity and broadening features. Also, during the transfer process at high surface pressure, it has been shown that the EHO molecules are ejected from the C8A monolayer and only a fraction of porphyrin is transferred to the solid support, in spite of a complete transfer for the C8A matrix. The complex structure of the reflection spectra at the air-water interface, as well as the polarization dependence of the absorption spectra for the mixed LB films, indicate the existence of four different arrangements for the EHO hosted in the C8A matrix. The aggregate formation is governed by two factors: the attraction between the porphyrin rings which minimizes their separation, and the alkyl chain interactions, that is, hydrophobic effect and/or steric hindrance which determine and restrict the possible aggregation structures. By using the extended dipole model, the assignment of the spectral peaks observed to different EHO aggregates is shown.

Astrobiological implications of dim light phototrophy in deep-sea red clays

NASA Astrophysics Data System (ADS)

Das, Anindita; Singh, Tanya; LokaBharathi, P. A.; Dhakephalkar, Prashant K.; Mallik, Sweta; Kshirsagar, Pranav R.; Khadge, N. H.; Nath, B. Nagender; Bhattacharya, Satadru; Dagar, Aditya Kumar; Kaur, Prabhjot; Ray, Dwijesh; Shukla, Anil D.; Fernandes, Christabelle E. G.; Fernandes, Sheryl O.; Thomas, Tresa Remya A.; Mamatha, S. S.; Mourya, Babu Shashikant; Meena, Ram Murti

2017-02-01

Red clays of Central Indian Basin (CIB) under influence of trace of Rodriguez Triple Junction exhibited chemoautotrophy, low temperature hydrothermal alterations and photoautotrophic potential. Seamount flank TVBC-08, hosting such signatures revealed dominance of aerobic anoxygenic phototroph Erythrobacter, with 93% of total 454 pyrosequencing tags. Subsequently, enrichments for both aerobic (Erythrobacter) and anaerobic anoxygenic phototrophs (green and purple sulphur bacteria) under red and white LED light illumination, with average irradiance 30.66 W m-2, were attempted for three red-clay sediment cores. Successful enrichments were obtained after incubation for c.a. 120 days at 4°± 2 °C and 25°± 2 °C, representing ambient psychrophilic and low temperature hydrothermal alteration conditions respectively. During hydrothermal cooling, a microbial succession from anaerobic chemolithotrophy to oxygenic photoautotrophy through anaerobic/aerobic anoxygenic phototrophic microbes is indicated. Spectral absorbance patterns of the methanol extracted cell pellets showed peaks corresponding to metal sulphide precipitations, the Soret band of chlorosome absorbance by photosystem II and absence of peaks at Qy transition band. Dendritic nano-structures of metal sulphides are common in these sediments and are comparable with other sulphidic paleo-marine Martian analogues. Significant blue and redshifts have been observed for the experimental samples relative to the un-inoculated medium. These observations indicate the propensity of metal-sulphide deposits contributing to chemiluminiscence supporting the growth of phototrophs at least partially, in the otherwise dark abyss. The effects of other geothermal heat and light sources are also under further consideration. The potential of phototrophic microbial cells to exhibit Doppler shift in absorbance patterns is significant towards understanding planetary microbial habitability. Planetary desiccation could considerably influence Doppler effects and consequently spectral detection techniques exo-planetary microbial life.

In-situ second harmonic generation by cancer cell targeting ZnO nanocrystals to effect photodynamic action in subcellular space.

PubMed

Gu, Bobo; Pliss, Artem; Kuzmin, Andrey N; Baev, Alexander; Ohulchanskyy, Tymish Y; Damasco, Jossana A; Yong, Ken-Tye; Wen, Shuangchun; Prasad, Paras N

2016-10-01

This paper introduces the concept of in-situ upconversion of deep penetrating near infrared light via second harmonic generation from ZnO nanocrystals delivered into cells to effect photo activated therapies, such as photodynamic therapy, which usually require activation by visible light with limited penetration through biological tissues. We demonstrated this concept by subcellular activation of a photodynamic therapy drug, Chlorin e6, excited within its strong absorption Soret band by the second harmonic (SH) light, generated at 409 nm by ZnO nanocrystals, which were targeted to cancer cells and internalized through the folate-receptor mediated endocytosis. By a combination of theoretical modeling and experimental measurements, we show that SH light, generated in-situ by ZnO nanocrystals significantly contributes to activation of photosensitizer, leading to cell death through both apoptotic and necrotic pathways initiated in the cytoplasm. This targeted photodynamic action was studied using label-free Coherent Anti-Stokes Raman Scattering imaging of the treated cells to monitor changes in the distribution of native cellular proteins and lipids. We found that initiation of photodynamic therapy with upconverted light led to global reduction in the intracellular concentration of macromolecules, likely due to suppression of proteins and lipids synthesis, which could be considered as a real-time indicator of cellular damage from photodynamic treatment. In prospective applications this in-situ photon upconversion could be further extended using ZnO nanocrystals surface functionalized with a specific organelle targeting group, provided a powerful approach to identify and consequently maximize a cellular response to phototherapy, selectively initiated in a specific cellular organelle. Copyright © 2016 Elsevier Ltd. All rights reserved.

Electrochemistry and electrocatalysis of myoglobin immobilized in sulfonated graphene oxide and Nafion films.

PubMed

Chen, Guiying; Sun, Hong; Hou, Shifeng

2016-06-01

In this study, sulfonated graphene oxide (SGO) was synthesized and characterized by Fourier transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS). It was used to make Mb-SGO-Nafion composite films by coating myoglobin (Mb) on the glassy carbon electrodes (GCE). Positions of the Soret absorption bands suggested that Mb retained its native conformation in the films. Mb-SGO-Nafion film modified electrode showed a pair of well-defined and nearly reversible cyclic voltammetry peaks at around -0.39 V versus saturated calomel electrode (SCE) in pH 7.0 buffers, characteristic of heme Fe(III)/Fe(II) redox couples. Electrochemical parameters such as electron transfer rate constant (ks) and formal potential (E(o')) were estimated by fitting the data of square-wave voltammetry with nonlinear regression analysis. Experimental data demonstrated that the electron transfer between Mb and electrode was greatly facilitated and showed good electrocatalytic properties toward various substrates, such as H2O2 and NaNO2, with significant lowering of reduction overpotential. Copyright © 2016. Published by Elsevier Inc.

The Fresnel Diffraction: A Story of Light and Darkness

NASA Astrophysics Data System (ADS)

Aime, C.; Aristidi, É.; Rabbia, Y.

2013-03-01

In a first part of the paper we give a simple introduction to the free space propagation of light at the level of a Master degree in Physics. The presentation promotes linear filtering aspects at the expense of fundamental physics. Following the Huygens-Fresnel approach, the propagation of the wave writes as a convolution relationship, the impulse response being a quadratic phase factor. We give the corresponding filter in the Fourier plane. As an illustration, we describe the propagation of wave with a spatial sinusoidal amplitude, introduce lenses as quadratic phase transmissions, discuss their Fourier transform properties and give some properties of Soret screens. Classical diffractions of rectangular diaphragms are also given here. In a second part of the paper, the presentation turns into the use of external occulters in coronagraphy for the detection of exoplanets and the study of the solar corona. Making use of Lommel series expansions, we obtain the analytical expression for the diffraction of a circular opaque screen, giving thereby the complete formalism for the Arago-Poisson spot. We include there shaped occulters. The paper ends up with a brief application to incoherent imaging in astronomy.

Electrostatic stabilization in sperm whale and harbor seal myoglobins

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

Gurd, F.R.N.; Friend, S.H.; Rothgeb, T.M.

1980-10-01

The compact, largely helical structure of sperm whale and harbor seal myoglobins undergoes an abrupt one-step transition between pH 4.5 and 3.5 as monitored by changes in either the heme Soret band absorbance or circular dichroism probes of secondary structure, for which a modified Tanford-Kirkwood theory provides identification of certain dominant electrostatic interactions responsible for the loss of stability. A similar treatment permits identification of the electrostatic interactions primarily responsible for a process in which the anchoring of the A helix to other parts of the molecule is weakened. This process is detected with both myoglobins, in a pH rangemore » approx. 1 unit higher than the onset of the overall unfolding process, through changes in the circular dichroic spectra near 295 nm which correspond to the L/sub a/O-O band of the only two tryptophan residues in these proteins, residues 7 and 14. In each case protonation of certain sites in neighboring parts of the molecule can be identified as producing destabilizing interactions with components of the A helix, particularly with lysine 16.« less

A spectroscopic study on the interaction between gold nanoparticles and hemoglobin

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

Garabagiu, Sorina, E-mail: sgarabagiu@itim-cj.ro

2011-12-15

Highlights: Black-Right-Pointing-Pointer The interaction was studied using UV-vis and fluorescence spectroscopy. Black-Right-Pointing-Pointer Gold nanoparticles quench the fluorescence emission of hemoglobin solution. Black-Right-Pointing-Pointer The binding and thermodynamic constants were calculated. Black-Right-Pointing-Pointer Major impact: electrochemical applications of the complex onto a substrate. -- Abstract: The interaction between horse hemoglobin and gold nanoparticles was studied using optical spectroscopy. UV-vis and fluorescence spectra show that a spontaneous binding process occurred between hemoglobin and gold nanoparticles. The Soret band of hemoglobin in the presence of gold nanoparticles does not show significant changes, which proves that the protein retained its biological function. A shift to longermore » wavelengths appears in the plasmonic band of gold nanoparticles upon the attachment of hemoglobin molecules. Gold nanoparticles quench the fluorescence emission of tryptophan residues in the structure of hemoglobin. The Stern-Volmer quenching constant, the binding constant and the number of binding sites were also calculated. Thermodynamic parameters indicate that the binding was mainly due to hydrophobic interactions.« less

Synthesis, optical and electrochemical properties of Zn-porphyrin for dye sensitized solar cell applications

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

Kotteswaran, S.; Pandian, M. Senthil; Ramasamy, P., E-mail: ramasamyp@ssn.edu.in

2016-05-23

Zn-Porphyrin dye has been synthesized by the reaction between aldehydes and pyrrole. The dye structure was confirmed by {sup 1}H NMR, {sup 13}C NMR spectrum. The functional group of the dye molecule was confirmed by FTIR spectrum. The UV-Vis-NIR absorption spectrum of Zn-Porphyrin in DMF solution was recorded in spectrophotometer. The UV-Vis NIR spectrum of dye exhibits a strong Soret band and Q-band. Cyclic Voltammograms were obtained with three electrode systems: Pt as counter electrode, saturated calomel used as a reference electrode and glassy carbon as working electrode at a scan rate of 100 mV/s. The curves recorded the oxidation ofmore » 0.5 mM compound Zn-Porphyrin in a dichloromethane solution containing 0.1M TBAP as supporting electrolyte, reveal two successive quasi reversible redox couples with the first anodic and cathodic peak potentials of -0.2 V and -1 V. The second anodic and cathodic peak potentials are 0.82 V and 0.01 V respectively.« less

Photoconductivity in DNA-Porphyrin Complexes

NASA Astrophysics Data System (ADS)

Myint, Peco; Oxford, Emma; Nyazenga, Collence; Smith, Walter; Qi, Zhengqing; Johnson, A. T.

2015-03-01

We have measured the photoconductivity of λ - DNA that is modified by intercalating a porphyrin compound, meso-tetrakis(N-methyl-4-pyridiniumyl)porphyrin (TMPyP), into its base stacks. Intercalation was verified by a red shift and hypochromism of the Soret absorption peak. The DNA/porphyrin strands were then deposited onto oxidized silicon substrates which had been patterned with interdigitated electrodes, and blown dry. Electrical measurements were carried out under nitrogen, using illumination from a 445 nm laser; this wavelength falls within the absorption peak of the DNA/porphyrin complexes. When initially measured under dry nitrogen, the complexes show no photoconductivity or dark conductivity. However, at relative humidities of 30% and above, we do observe dark conductivity, and also photoconductivity that grows with time. Photoconductivity gets larger at higher relative humidity. Remarkably, when the humidity is lowered again, some photoconductivity is now observed, indicating a change that persists for more than 24 hours. It may be that the humidity alters the structure of the DNA, perhaps allowing for better alignment of the bases. This work was supported by NSF Grant BMAT-1306170.

Theoretical studies in support of the 3M-vapor transport (PVTOS-) experiments

NASA Technical Reports Server (NTRS)

Rosner, Daniel E.; Keyes, David E.

1989-01-01

Results are reported for a preliminary theoretical study of the coupled mass-, momentum-, and heat-transfer conditions expected within small ampoules used to grow oriented organic solid (OS-) films, by physical vapor transport (PVT) in microgravity environments. It is show that previous studies made restrictive assumptions (e.g., smallness of delta T/T, equality of molecular diffusivities) not valid under PVTOS conditions, whereas the important phenomena of sidewall gas creep, Soret transport of the organic vapor, and large vapor phase supersaturations associated with the large prevailing temperature gradients were not previously considered. Rational estimates are made of the molecular transport properties relevant to copper-phthalocyanine monomeric vapor in a gas mixture containing H2(g) and Xe(g). Efficient numerical methods have been developed and are outlined/illustrated here to making steady axisymmetric gas flow calculations within such ampoules, allowing for realistic realistic delta T/T(sub)w-values, and even corrections to Navier-Stokes-Fourier 'closure' for the governing continuum differential equations. High priority follow-on studies are outlined based on these new results.

Optothermal Manipulations of Colloidal Particles and Living Cells.

PubMed

Lin, Linhan; Hill, Eric H; Peng, Xiaolei; Zheng, Yuebing

2018-05-25

Optical manipulation techniques are important in many fields. For instance, they enable bottom-up assembly of nanomaterials and high-resolution and in situ analysis of biological cells and molecules, providing opportunities for discovery of new materials, medical diagnostics, and nanomedicines. Traditional optical tweezers have their applications limited due to the use of rigorous optics and high optical power. New strategies have been established for low-power optical manipulation techniques. Optothermal manipulation, which exploits photon-phonon conversion and matter migration under a light-controlled temperature gradient, is one such emerging technique. Elucidation of the underlying physics of optothermo-matter interaction and rational engineering of optical environments are required to realize diverse optothermal manipulation functionalities. This Account covers the working principles, design concepts, and applications of a series of newly developed optothermal manipulation techniques, including bubble-pen lithography, opto-thermophoretic tweezers, opto-thermoelectric tweezers, optothermal assembly, and opto-thermoelectric printing. In bubble-pen lithography, optical heating of a plasmonic substrate generates microbubbles at the solid-liquid interface to print diverse colloidal particles on the substrates. Programmable bubble printing of semiconductor quantum dots on different substrates and haptic control of printing have also been achieved. The key to optothermal tweezers is the ability to deliver colloidal particles from cold to hot regions of a temperature gradient or a negative Soret effect. We explore different driving forces for the two types of optothermal tweezers. Opto-thermophoretic tweezers rely on an abnormal permittivity gradient built by structured solvent molecules in the electric double layer of colloidal particles and living cells in response to heat-induced entropy, and opto-thermoelectric tweezers exploit a thermophoresis-induced thermoelectric field for the low-power manipulation of small nanoparticles with minimum diameter around 20 nm. Furthermore, by incorporating depletion attraction into the optothermal tweezers system as particle-particle or particle-substrate binding force, we have achieved bottom-up assembly and reconfigurable optical printing of artificial colloidal matter. Beyond optothermal manipulation techniques in liquid environments, we also review recent progress of gas-phase optothermal manipulation based on photophoresis. Photophoretic trapping and transport of light-absorbing materials have been achieved through optical engineering to tune particle-molecule interactions during optical heating, and a novel optical trap display has been demonstrated. An improved understanding of the colloidal response to temperature gradients will surely facilitate further innovations in optothermal manipulation. With their low-power operation, simple optics, and diverse functionalities, optothermal manipulation techniques will find a wide range of applications in life sciences, colloidal science, materials science, and nanoscience, as well as in the developments of colloidal functional devices and nanomedicine.

Trojan Horse for Light-Triggered Bifurcated Production of Singlet Oxygen and Fenton-Reactive Iron within Cancer Cells.

PubMed

Cioloboc, Daniela; Kennedy, Christopher; Boice, Emily N; Clark, Emily R; Kurtz, Donald M

2018-01-08

Traditional photodynamic therapy for cancer relies on dye-photosensitized generation of singlet oxygen. However, therapeutically effective singlet oxygen generation requires well-oxygenated tissues, whereas many tumor environments tend to be hypoxic. We describe a platform for targeted enhancement of photodynamic therapy that produces singlet oxygen in oxygenated environments and hydroxyl radical, which is typically regarded as the most toxic reactive oxygen species, in hypoxic environments. The 24-subunit iron storage protein bacterioferritin (Bfr) has the unique property of binding 12 heme groups in its protein shell. We inserted the isostructural photosensitizer, zinc(II) protoporphyrin IX (ZnP), in place of the hemes and extended the surface-exposed N-terminal ends of the Bfr subunits with a peptide targeting a receptor that is hyperexpressed on the cell surface of many tumors and tumor vasculature. We then loaded the inner cavity with ∼2500 irons as a ferric oxyhydroxide polymer and finally conjugated 2 kDa polyethylene glycol to the outer surface. We showed that the inserted ZnP photosensitizes generation of both singlet oxygen and the hydroxyl radical, the latter via the reaction of photoreleased ferrous iron with hydrogen peroxide. This targeted iron-loaded ZnP-Bfr construct was endocytosed by C32 melanoma cells and localized to lysosomes. Irradiating the treated cells with light at wavelengths overlapping the ZnP Soret absorption band induced photosensitized intracellular Fe 2+ release and substantial lowering of cell viability. This targeted, light-triggered production of intracellular singlet oxygen and Fenton-reactive iron could potentially be developed into a phototherapeutic adjunct for many types of cancers.

Pigment spectra and intermolecular interaction potentials in glasses and proteins.

PubMed

Renge, I; van Grondelle, R; Dekker, J P

2007-10-01

A model is proposed for chromophore optical spectra in solids over a wide range of temperatures and pressures. Inhomogeneous band shapes and their pressure dependence, as well as baric shift coefficients of spectral lines, selected by the frequency, were derived using Lennard-Jones potentials of the ground and excited states. Quadratic electron-phonon coupling constants, describing the thermal shift and broadening of zero-phonon lines, were also calculated. Experimentally, thermal shift and broadening of spectral holes were studied between 5 and 40 K for a synthetic pigment, chlorin, embedded in polymer hosts. The baric effects on holes were determined by applying hydrostatic He gas pressure up to 200 bar, at 6 K. Absorption spectra of pheophytin a, chlorophyll a, and beta-carotene in polymers and plant photosystem II CP47 complex were measured between 5 (or 77) and 300 K, and subject to Voigtian deconvolution. A narrowing of inhomogeneous bandwidth with increasing temperature, predicted on the basis of hole behavior, was observed as the shrinking of Gaussian spectral component. The Lorentzian broadening was ascribed to optical dephasing up to 300 K in transitions with weak to moderate linear electron-phonon coupling strength. The thermal broadening is purely Gaussian in multiphonon transitions (S(2) band of beta-carotene, Soret bands of tetrapyrrolic pigments), and the Lorentz process appears to be suppressed, indicating a lack of exponential dephasing. Density, polarity, polarizability, compressibility, and other local parameters of the pigment binding sites in biologically relevant systems can be deduced from spectroscopic data, provided that sufficient background information is available.

Pigment Spectra and Intermolecular Interaction Potentials in Glasses and Proteins

PubMed Central

Renge, I.; van Grondelle, R.; Dekker, J. P.

2007-01-01

A model is proposed for chromophore optical spectra in solids over a wide range of temperatures and pressures. Inhomogeneous band shapes and their pressure dependence, as well as baric shift coefficients of spectral lines, selected by the frequency, were derived using Lennard-Jones potentials of the ground and excited states. Quadratic electron-phonon coupling constants, describing the thermal shift and broadening of zero-phonon lines, were also calculated. Experimentally, thermal shift and broadening of spectral holes were studied between 5 and 40 K for a synthetic pigment, chlorin, embedded in polymer hosts. The baric effects on holes were determined by applying hydrostatic He gas pressure up to 200 bar, at 6 K. Absorption spectra of pheophytin a, chlorophyll a, and β-carotene in polymers and plant photosystem II CP47 complex were measured between 5 (or 77) and 300 K, and subject to Voigtian deconvolution. A narrowing of inhomogeneous bandwidth with increasing temperature, predicted on the basis of hole behavior, was observed as the shrinking of Gaussian spectral component. The Lorentzian broadening was ascribed to optical dephasing up to 300 K in transitions with weak to moderate linear electron-phonon coupling strength. The thermal broadening is purely Gaussian in multiphonon transitions (S2 band of β-carotene, Soret bands of tetrapyrrolic pigments), and the Lorentz process appears to be suppressed, indicating a lack of exponential dephasing. Density, polarity, polarizability, compressibility, and other local parameters of the pigment binding sites in biologically relevant systems can be deduced from spectroscopic data, provided that sufficient background information is available. PMID:17557783

Heme Distortions in Sperm-Whale Carbonmonoxy Myoglobin: Correlations between Rotational Strengths and Heme Distortions in MD-Generated Structures

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

KIEFL,CHRISTOPH; SCREERAMA,NARASIMHA; LU,YI

2000-07-13

The authors have investigated the effects of heme rotational isomerism in sperm-whale carbonmonoxy myoglobin using computational techniques. Several molecular dynamics simulations have been performed for the two rotational isomers A and B, which are related by a 180{degree} rotation around the {alpha}-{gamma} axis of the heme, of sperm-whale carbonmonoxy myoglobin in water. Both neutron diffraction and NMR structures were used as starting structures. In the absence of an experimental structure, the structure of isomer B was generated by rotating the heme in the structure of isomer A. Distortions of the heme from planarity were characterized by normal coordinate structural decompositionmore » and by the angle of twist of the pyrrole rings from the heme plane. The heme distortions of the neutron diffraction structure were conserved in the MD trajectories, but in the NMR-based trajectories, where the heme distortions are less well defined, they differ from the original heme deformations. The protein matrix induced similar distortions on the heroes in orientations A and B. The results suggest that the binding site prefers a particular macrocycle conformation, and a 180{degree} rotation of the heme does not significantly alter the protein's preference for this conformation. The intrinsic rotational strengths of the two Soret transitions, separated according to their polarization in the heme plane, show strong correlations with the ruf-deformation and the average twist angle of the pyrrole rings. The total rotational strength, which includes contributions from the chromophores in the protein, shows a weaker correlation with heme distortions.« less

New preparation based on coproporphyrin III for photoluminescence diagnostics and photodynamic therapy

NASA Astrophysics Data System (ADS)

Belousova, I. M.; Dobrun, M. V.; Galebskaya, L. V.; Gorelov, S. I.; Kislyakov, I. M.; Kolbasov, S. E.; Kris'ko, A. V.; Kris'ko, T. K.; Malkov, M. A.; Murav'eva, T. D.; Petrishchev, N. N.

2011-03-01

We resume a complex study of a new Coproporphyrin III preparation obtained in vitro via microbiological synthesis in environment of a cultural medium of Arthrobacter globiformis with gaining of the coproporphyrin III tetrapotash salt sterilized aqueous solution with 94.5% purity. The main impurities have porphyrinic nature. The absorption spectrum shows that the preparation has multiple excitation bands in visible region with most pronounced maxima at 501 nm, 535 nm, and 556 nm, and a weak one at 606 nm. The most effective spectral range of its electronic states excitation can serve the region of a Soret band with maximum at 404 nm. Comparative luminescent and photosensitizing properties of Coproporphyrin III and Fotoditazin preparations have been studied. Luminescence and singlet oxygen quantum yields have been determined to be 0.03 and 0.37 (Coproporphyrin III) and 0.05 and 0.6 (Fotoditazin) correspondingly. A reduction of the quantum yields values at an introduction of a biological additive into aqueous solutions of the given preparations has been found. Preclinical trials of the preparation are performed. It is shown that Coproporphyrin III toxicity value is LD50 = 2400 +/- 120 mg/kg, that allows to rank this preparation to the (V) class of almost nontoxical medicinal agents. It is shown that the preparation Coproporphyrin III has no teratogenic and allergenic properties and does not damage erythrocytes and thrombocytes. Absence of an influence of the preparation on the blood flow speed has been established. The results obtained thereby testify the absence of contra-indications for clinical tests of the Coproporphyrin III preparation on indicators of sharp toxicity.

Spectroscopic Study of the Interaction between Horse Heart Myoglobin and Zirconium(IV)-Substituted Polyoxometalates as Artificial Proteases.

PubMed

Ly, Hong Giang T; Parac-Vogt, Tatjana N

2017-09-20

A recent study [Angew. Chem. Int. Ed. 2015, 54, 7391-7394] has shown that horse heart myoglobin (HHM) is selectively hydrolyzed by a range of zirconium(IV)-substituted polyoxometalates (POMs) under mild conditions. In this study, the molecular interactions between the Zr-POM catalysts and HHM are investigated by using a range of complementary techniques, including circular dichroism (CD), UV/Vis spectroscopy, tryptophan fluorescence spectroscopy, and 1 H and 31 P NMR spectroscopy. A tryptophan fluorescence quenching study reveals that, among all examined Zr-POMs, the most reactive POM, 2:2 Zr IV -Keggin, exhibits the strongest interaction with HHM. 31 P NMR spectroscopy studies show that this POM dissociates in solution, resulting in the formation of a monomeric 1:1 Zr IV -Keggin structure, which is likely to be a catalytically active species. In the presence of Zr IV -POMs, HHM does not undergo complete denaturation, as evidenced by CD, UV/Vis, tryptophan fluorescence, and 1 H NMR spectroscopy. CD spectroscopy shows a gradual decrease in the α-helical content of HHM upon addition of Zr IV -POMs. The largest effect is observed in the presence of a large Zr IV -Wells-Dawson structure, whereas small Zr IV -Lindqvist POM has the least influence on the decrease in the α-helical content of HHM. In all cases, the Soret band at λ=409 nm is maintained in the presence of all examined Zr-POMs, which indicates that no conformational changes in the protein occur near the heme group. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Comparison between chlorosomes containing bacteriochlorophyll-c and chlorosomes containing bacteriochlorophyll-d isolated from two substrains of green sulfur photosynthetic bacterium Chlorobium vibrioforme NCIB 8327.

PubMed

Saga, Yoshitaka; Tamiaki, Hitoshi

2004-07-19

Chlorosomes containing bacteriochlorophyll(BChl)-c and those containing BChl-d were isolated from two substrains of Chlorobium vibrioforme f. sp. thiosulfatophilum NCIB 8327, respectively. The two types of chlorosomes were investigated from the following aspect, what kinds of effects the molecular structure of chlorosomal BChls had on structural and spectroscopic properties of in vivo self-aggregates in chlorosomes without alteration of the other components such as chlorosomal proteins and lipids; both chlorosomes were expected to have the same components except for light-harvesting BChls. In their visible absorption spectra, the differences of Soret and Q(y) peak positions between BChl-c containing and BChl-d containing chlorosomes were similar to the differences between monomeric BChl-c and d. An inverse S-shaped CD signal in the Q(y) region of BChl-d containing chlorosomes was 1.4 times larger than that of BChl-c containing chlorosomes, when the Q(y) absorbance of the two chlorosomes was almost the same. This implies that the excitonic interaction of BChl-d is larger than that of BChl-c in natural chlorosomes. Resonance Raman spectroscopy showed that BChl self-assemblies in both chlorosomes were essentially formed by the same local structural interaction among 3(1)-hydroxy group, 13-keto group, and central magnesium. BChl-d self-aggregates in chlorosomes were more tolerant of 1-hexanol than in vivo BChl-c aggregates, suggesting that the molecular structure of BChl-d provided more stable self-assemblies than BChl-c in natural chlorosomes.

Resonance and Variable Temperature Raman Studies of Chloroperoxidase and Methemoglobin.

NASA Astrophysics Data System (ADS)

Remba, Ronald David

1980-12-01

Raman spectra of the heme proteins chloroperoxidase and methemoglobin, chemically and temperature modified, are obtained for laser excitation near the Soret absorption band. Numerous biochemical and physical results are obtained. The following observations for chloroperoxidase have been made. The scattered intensity for resonance (406.7 nm) excitation is at least twenty times that for near resonance (457.9 nm) excitation. In resonance only totally symmetric modes are enhanced. The positions of marker band I ((TURN) 1370 cm(' -1)) for both the native and reduced enzymes are lower than expected for high-spin heme proteins indicating a strongly electron donating axial ligand. From shifts in spin-sensitive Raman peaks as the temperature is lowered, a high-spin to low-spin transition of the heme iron is inferred. Raman spectra of chloroperoxidase liganded with small ions indicate that there is a second anion binding site near the heme. Photo-dissociation of CO from reduced chloroperoxidase is observed. The position of marker band I in the CO complex indicates that electron density is transferred from the heme onto the CO. The resonance Raman spectra of chloroperoxidase and cytochrome P-450 are nearly identical and are very different from those of horseradish peroxidase and cytochrome c. These results, particularly for the reduced enzymes, indicate that the heme sites in chloroperoxidase and P -450 are essentially the same. Raman spectra of a number of methemoglobins complexed with various small ions are obtained as a function of temperature in the region of spin-sensitive marker band (II) ((TURN) 1500 cm('-1)) for laser excitation near the Soret absorption band. For certain ligands, H(,2)O, N(,3)('-), OCN('-), OH('-) and SCN('-), the iron spin state changes from high spin to low spin with decreasing temperature. The relative spin concentrations are monitored by measuring the Raman intensity ratio, I(,h)/I(,1), of the high-spin and low -spin versions of marker band (II) as a function of temperature. This is the first study where the marker band technique is used to measure quantitatively spin transitions. For hydroxide and cyanate methemoglobin, log(I(,h)/I(,1)) varies linearly with 1/T, indicating a high-spin/low-spin thermal equilibrium. The data are analyzed to extract enthalpic and entropic changes. (DELTA)H values from Raman and static magnetic susceptibility techniques show good agreement. (DELTA)S values for horse hydroxide methemoglobin also agree. However, for cyanate methemoglobin, Raman and susceptibility (DELTA)S values differ substantially. Other evidence (ESR, optical, etc.) supports the Raman result. The discrepancy is probably due to the effects of freezing on the protein solution. Other methemoglobins show a discontinuity in the Raman intensity ratio at the freezing transition indicating a non-equilibrium situation where the freezing process drives the spin transition. Effects of freezing the protein solution on the spin transition are discussed. Both the high-spin and low-spin Raman frequencies are observed to remain constant (within (+OR-) 2 cm('-1)) when the temperature is varied. This is discussed in terms of core expansion and heme deformation. Experimental (DELTA)S values are much larger than the spin-only value. This is discussed in terms of a linear temperature dependence on the energy gap between the ('2)T(,2) ground state and the ('6)A(,1) first excited state. Variable temperature Raman data for carp azide methemoglobin with and without IHP indicate that the free energy for the spin transition decreases by 0.6 (+OR-) 0.3 kcal/mole when hemoglobin quaternary structure changes from R to T. Lack of any frequency shift in either the high-spin or low-spin Raman band upon addition of IHP is consistent with other evidence indicating no iron movement upon conversion of R to T quaternary forms.

The (oxo)[(2,3,7,8,12,13,17,18-octachloro-5,10,15,20-tetrakis(4-tolylporphyrinato)]vanadium(IV): Synthesis, UV-visible, Cyclic voltammetry and X-ray crystal structure

NASA Astrophysics Data System (ADS)

Mchiri, Chadlia; Amiri, Nesrine; Jabli, Souhir; Roisnel, Thierry; Nasri, Habib

2018-02-01

The present work is concerned with the oxo vanadium(IV) complex of 2,3,7,8,12,13,17,18-octachloro-5,10,15,20-tetrakis(4-tolylporphyrin) with formula [V(Cl8TTP)O] (I), which was prepared by reacting the (oxo)[5,10,15,20-tetrakis(4-tolylporphyrinato)]vanadium(IV) complex ([V(TTP)O]), under aerobic atmosphere, with a large excess of thionyl chloride (SOCl2). The title compound was characterized by UV-visible spectroscopy, cyclic voltammetry and X-ray crystal structure. The electron-withdrawing chlorine substituents at the pyrrole carbons in the vanadyl-Cl8TTP derivative produce remarkable redshifts of the Soret and Q absorption bands and an important anodic shift of the porphyrin ring oxidation and reduction potentials. This is an indication that the porphyrin core of complex (I) is severely nonplanar in solution. The molecular structure of our vanadyl derivative shows a very high saddle distortion and an important ruffled deformation of the porphyrin macrocycle. The crystal structure of (I) is made by one-dimensional chains parallel to the c axis where channels are located between these chains.

Thin Fresnel zone plate lenses for focusing underwater sound

NASA Astrophysics Data System (ADS)

Calvo, David C.; Thangawng, Abel L.; Nicholas, Michael; Layman, Christopher N.

2015-07-01

A Fresnel zone plate (FZP) lens of the Soret type creates a focus by constructive interference of waves diffracted through open annular zones in an opaque screen. For underwater sound below MHz frequencies, a large FZP that blocks sound using high-impedance, dense materials would have practical disadvantages. We experimentally and numerically investigate an alternative approach of creating a FZP with thin (0.4λ) acoustically opaque zones made of soft silicone rubber foam attached to a thin (0.1λ) transparent rubber substrate. An ultra-thin (0.0068λ) FZP that achieves higher gain is also proposed and simulated which uses low-volume fraction, bubble-like resonant air ring cavities to construct opaque zones. Laboratory measurements at 200 kHz indicate that the rubber foam can be accurately modeled as a lossy fluid with an acoustic impedance approximately 1/10 that of water. Measured focal gains up to 20 dB agree with theoretical predictions for normal and oblique incidence. The measured focal radius of 0.68λ (peak-to-null) agrees with the Rayleigh diffraction limit prediction of 0.61 λ/NA (NA = 0.88) for a low-aberration lens.

Stabilizing g-States in Centrosymmetric Tetrapyrroles: Two-Photon-Absorbing Porphyrins with Bright Phosphorescence.

PubMed

Esipova, Tatiana V; Rivera-Jacquez, Héctor J; Weber, Bruno; Masunov, Artëm E; Vinogradov, Sergei A

2017-08-24

Using time-dependent density functional theory (TDDFT) and sum-overstates (SOS) formalism, we predicted significant stabilization of 2P-active g-states in a compact fully symmetric porphyrin, in which all four pyrrolic fragments are fused with phathalimide residues via the β-carbon positions. The synthesis of a soluble, nonaggregating meso-unsubstituted tetraarylphthalimidoporphyrin (TAPIP) was then developed, and the spectroscopic measurements confirmed that a strongly 2P-active state in this porphyrin is stabilized below the B (Soret) state level. Single-crystal X-ray analysis revealed near-ideally planar geometry of the TAPIP macrocycle, while its tetra-meso-arylated analogue (meso-Ar 4 TAPIP) was found to be highly saddled. Consistent with these structural features, Pt meso-Ar 4 TAPIP phosphoresces rather weakly (ϕ phos = 0.05 in DMF at 22 °C), while both Pt and Pd complexes of TAPIP are highly phosphorescent (ϕ phos = 0.45 and 0.23, respectively). In addition PdTAPIP exhibits non-negligible thermally activated (E-type) delayed fluorescence (ϕ fl (d) ∼ 0.012). Taken together, these photophysical properties make metal complexes of meso-unsubstituted tetaarylphthalimidoporphyrins the brightest 2P-absorbing phosphorescent chromophores known to date.

Thin Fresnel zone plate lenses for focusing underwater sound

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

Calvo, David C., E-mail: david.calvo@nrl.navy.mil; Thangawng, Abel L.; Nicholas, Michael

A Fresnel zone plate (FZP) lens of the Soret type creates a focus by constructive interference of waves diffracted through open annular zones in an opaque screen. For underwater sound below MHz frequencies, a large FZP that blocks sound using high-impedance, dense materials would have practical disadvantages. We experimentally and numerically investigate an alternative approach of creating a FZP with thin (0.4λ) acoustically opaque zones made of soft silicone rubber foam attached to a thin (0.1λ) transparent rubber substrate. An ultra-thin (0.0068λ) FZP that achieves higher gain is also proposed and simulated which uses low-volume fraction, bubble-like resonant air ringmore » cavities to construct opaque zones. Laboratory measurements at 200 kHz indicate that the rubber foam can be accurately modeled as a lossy fluid with an acoustic impedance approximately 1/10 that of water. Measured focal gains up to 20 dB agree with theoretical predictions for normal and oblique incidence. The measured focal radius of 0.68λ (peak-to-null) agrees with the Rayleigh diffraction limit prediction of 0.61 λ/NA (NA = 0.88) for a low-aberration lens.« less

[Spectral properties of new photosensitizers for photodynamic diagnosis and therapy].

PubMed

Li, Bu-hong; Xie, Shu-sen; Lu, Zu-kang

2002-12-01

The spectral properties of new photosensitizer ZnPcS2P2, PsD-007 and HMME, as well as traditional photosensitizer HpD have been studied by comparing their spectra in physiological saline and in physiological saline with 10 percent serum. Experimental results show that the maximum absorption peaks for PsD-007, HMME and HpD in the physiological saline with 10 percent serum appear at 400 nm in the soret region, while at 670 nm for ZnPcS2P2. The fluorescence excitation spectra closely resemble the absorption spectra. When excited by the light at the wavelengths of 413 and 514.5 nm, the fluorescence emission peaks for PsD-007, HMME and HpD appear at 625 and 690 nm, respectively. The fluorescent excitation efficiency of the same photosensitizer with the same concentration excited by the light at the wavelength of 413 nm is about three fold higher than that at 514.5 nm. Furthermore, the fluorescent excitation efficiency is the highest for HMME, but is lower for HpD and lowest for PsD-007. These results are significant in the selection of photosensitizers for photodynamic diagnosis and therapy.

Ratiometric Fluorescent Detection of Pb2+ by FRET-Based Phthalocyanine-Porphyrin Dyads.

PubMed

Zhang, Dongli; Zhu, Mengliang; Zhao, Luyang; Zhang, Jinghui; Wang, Kang; Qi, Dongdong; Zhou, Yang; Bian, Yongzhong; Jiang, Jianzhuang

2017-12-04

Sensitive and selective detection of Pb 2+ is a very worthwhile endeavor in terms of both human health and environmental protection, as the heavy metal is fairly ubiquitous and highly toxic. In this study, we designed phthalocyanine-porphyrin (Pc-Por) heterodyads, namely, H 2 Pc-α-ZnPor (1) and H 2 Pc-β-ZnPor (2), by connecting a zinc(II) porphyrin moiety to the nonperipheral (α) or peripheral (β) position of a metal-free phthalocyanine moiety. Upon excitation at the porphyrin Soret region (420 nm), both of the dyads exhibited not only a porphyrin emission (605 nm) but also a phthalocyanine emission (ca. 700 nm), indicating the occurrence of intramolecular fluorescence resonance energy transfer (FRET) processes from the porphyrin donor to the phthalocyanine acceptor. The dyads can selectively bind Pb 2+ in the phthalocyanine core leading to a red shift of the phthalocyanine absorption and thus a decrease of spectral overlap between the porphyrin emission and phthalocyanine absorption, which in turn suppresses the intramolecular FRET. In addition, the binding of Pb 2+ can highly quench the emission of phthalocyanine by heavy-metal ion effects. The synergistic coupled functions endow the dyads with remarkable ratiometric fluorescent responses at two distinct wavelengths (F 605 /F 703 for 1 and F 605 /F 700 for 2). The emission intensity ratio increased as a linear function to the concentration of Pb 2+ in the range of 0-4.0 μM, whereas the detection limits were determined to be 3.4 × 10 -9 and 2.2 × 10 -8 M for 1 and 2, respectively. Furthermore, by comparative study of 1 and 2, the effects of distance and relative orientation between Pc and ZnPor fluorophores on the FRET efficiency and sensing performance were highlighted, which is helpful for further optimizing such FRET systems.

Astrobiological implications of dim light phototrophy in deep-sea red clays.

PubMed

Das, Anindita; Singh, Tanya; LokaBharathi, P A; Dhakephalkar, Prashant K; Mallik, Sweta; Kshirsagar, Pranav R; Khadge, N H; Nath, B Nagender; Bhattacharya, Satadru; Dagar, Aditya Kumar; Kaur, Prabhjot; Ray, Dwijesh; Shukla, Anil D; Fernandes, Christabelle E G; Fernandes, Sheryl O; Thomas, Tresa Remya A; S S, Mamatha; Mourya, Babu Shashikant; Meena, Ram Murti

2017-02-01

Red clays of Central Indian Basin (CIB) under influence of trace of Rodriguez Triple Junction exhibited chemoautotrophy, low temperature hydrothermal alterations and photoautotrophic potential. Seamount flank TVBC-08, hosting such signatures revealed dominance of aerobic anoxygenic phototroph Erythrobacter, with 93% of total 454 pyrosequencing tags. Subsequently, enrichments for both aerobic (Erythrobacter) and anaerobic anoxygenic phototrophs (green and purple sulphur bacteria) under red and white LED light illumination, with average irradiance 30.66Wm -2 , were attempted for three red-clay sediment cores. Successful enrichments were obtained after incubation for c.a. 120 days at 4°± 2°C and 25°± 2°C, representing ambient psychrophilic and low temperature hydrothermal alteration conditions respectively. During hydrothermal cooling, a microbial succession from anaerobic chemolithotrophy to oxygenic photoautotrophy through anaerobic/aerobic anoxygenic phototrophic microbes is indicated. Spectral absorbance patterns of the methanol extracted cell pellets showed peaks corresponding to metal sulphide precipitations, the Soret band of chlorosome absorbance by photosystem II and absence of peaks at Qy transition band. Dendritic nano-structures of metal sulphides are common in these sediments and are comparable with other sulphidic paleo-marine Martian analogues. Significant blue and redshifts have been observed for the experimental samples relative to the un-inoculated medium. These observations indicate the propensity of metal-sulphide deposits contributing to chemiluminiscence supporting the growth of phototrophs at least partially, in the otherwise dark abyss. The effects of other geothermal heat and light sources are also under further consideration. The potential of phototrophic microbial cells to exhibit Doppler shift in absorbance patterns is significant towards understanding planetary microbial habitability. Planetary desiccation could considerably influence Doppler effects and consequently spectral detection techniques exo-planetary microbial life. Copyright © 2017 The Committee on Space Research (COSPAR). Published by Elsevier Ltd. All rights reserved.

Fluctuations in diffusion processes in microgravity.

PubMed

Mazzoni, Stefano; Cerbino, Roberto; Vailati, Alberto; Giglio, Marzio

2006-09-01

It has been shown recently that diffusion processes exhibit giant nonequilibrium fluctuations (NEFs). That is, the diffusing fronts display corrugations whose length scale ranges from the molecular to the macroscopic one. The amplitude of the NEF diverges following a power law behavior proportional to q(-4) (where q is the wave vector). However, fluctuations of wave number smaller than a critical "rolloff" wave vector are quenched by the presence of gravity. It is therefore expected that in microgravity conditions, the amplitude of the NEF should be boosted by the absence of the buoyancy-driven restoring force. This may affect any diffusion process performed in microgravity, such as the crystallization of a protein solution induced by the diffusion of a salt buffer. The aim of GRADFLEX (GRAdient-Driven FLuctuation EXperiment), a joint project of ESA and NASA, is to investigate the presence of NEFs arising in a diffusion process under microgravity conditions. The project consists of two experiments. One is carried out by UNIMI (University of Milan) and INFM (Istituto Nazionale per la Fisica della Materia) and is focused on NEF in a concentration diffusion process. The other experiment is performed by UCSB (University of California at Santa Barbara) concerning temperature NEF in a simple fluid. In the UNIMI part of the GRADFLEX experimental setup, NEFs are induced in a binary mixture by means of the Soret effect. The diagnostic method is an all-optical quantitative shadowgraph technique. The power spectrum of the induced NEFs is obtained by the processing of the shadowgraph images. A detailed description of the experimental apparatus as well as the ground-based experimental results is presented here for the UNIMI-INFM experiment. The GRADFLEX payload is scheduled to fly on the FOTON M3 capsule in April 2007.

Origin of heavy Fe isotope compositions in high-silica igneous rocks: A rhyolite perspective

NASA Astrophysics Data System (ADS)

Du, De-Hong; Wang, Xiao-Lei; Yang, Tao; Chen, Xin; Li, Jun-Yong; Li, Weiqiang

2017-12-01

The origin of heavy Fe isotope compositions in high-silica (>70 wt% SiO2) igneous rocks remains a highly controversial topic. Considering that fluid exsolution in eruptive rocks is more straight-forward to constrain than in plutonic rocks, this study addresses the problem of Fe isotope fractionation in high-silica igneous rocks by measuring Fe isotope compositions of representative rhyolitic samples from the Neoproterozoic volcanic-sedimentary basins in southern China and the Triassic Tu Le Basin in northern Vietnam. The samples show remarkably varied δ56FeIRMM014 values ranging from 0.05 ± 0.05‰ to 0.55 ± 0.05‰, which is among the highest values reported from felsic rocks. The extensional tectonic setting and short melt residence time in magma chambers for the studied rhyolites rule out Soret diffusion and thermal migration processes as causes of the high δ56Fe values. Effects of volcanic degassing and fluid exsolution on bulk rock δ56Fe values for the rhyolites are also assessed using bulk rock geochemical indicators and Rayleigh fractionation models, and these processes are found to be insufficient to produce resolvable changes in Fe isotope compositions of the residual melt. The most probable mechanism accounting for heavy Fe isotope compositions in the high-silica rhyolites is narrowed down to fractional crystallization processes in the magma before rhyolite eruption. Removal of isotopically light Fe-bearing minerals (i.e. ulvöspinel-rich titanomagnetite, ilmenite and biotite) is proposed as the main cause of Fe isotope variation in silicic melts during magmatic evolution. This study implies that crystal fractionation is the dominant mechanism that controls Fe isotope fractionation in eruptive rocks and Fe isotopes could be used to study magmatic differentiation of high-silica magmas.

Femtosecond fluorescence dynamics of porphyrin in solution and solid films: the effects of aggregation and interfacial electron transfer between porphyrin and TiO2.

PubMed

Luo, Liyang; Lo, Chen-Fu; Lin, Ching-Yao; Chang, I-Jy; Diau, Eric Wei-Guang

2006-01-12

The excited-state relaxation dynamics of a synthetic porphyrin, ZnCAPEBPP, in solution, coated on a glass substrate as solid films, mixed with PMMA and coated on a glass substrate as solid films, and sensitized on nanocrystalline TiO2 films were investigated by using femtosecond fluorescence up-conversion spectroscopy with excitation in the Soret band, S2. We found that the S2--> S1 electronic relaxation of ZnCAPEBPP in solution and on PMMA films occurs in 910 and 690 fs, respectively, but it becomes extremely rapid, <100 fs, in solid films and TiO2 films due to formation of porphyrin aggregates. When probed in the S1 state of porphyrin, the fluorescence transients of the solid films show a biphasic kinetic feature with the rapid and slow components decaying in 1.9-2.4 and 19-26 ps, respectively. The transients in ZnCAPEBPP/TiO2 films also feature two relaxation processes but they occur on different time scales, 100-300 fs and 0.8-4.1 ps, and contain a small offset. According to the variation of relaxation period as a function of molecular density on a TiO2 surface, we assigned the femtosecond component of the TiO2 films as due to indirect interfacial electron transfer through a phenylethynyl bridge attached to one of four meso positions of the porphyrin ring, and the picosecond component arising from intermolecular energy transfer among porphyrins. The observed variation of aggregate-induced relaxation periods between solid and TiO2 films is due mainly to aggregation of two types: J-type aggregation is dominant in the former case whereas H-type aggregation prevails in the latter case.

Charge transport in organic multi-layer devices under electric and optical fields

NASA Astrophysics Data System (ADS)

Park, June Hyoung

2007-12-01

Charge transport in small organic molecules and conjugated conducting polymers under electric or optical fields is studied by using field effect transistors and photo-voltaic cells with multiple thin layers. With these devices, current under electric field, photo-current under optical field, and luminescence of optical materials are measured to characterize organic and polymeric materials. For electric transport studies, poly(3,4-ethylenedioxythiophene) doped by polystyrenesulfonic acid is used, which is conductive with conductivity of approximately 25 S/cm. Despite their high conductance, field effect transistors based on the films are successfully built and characterized by monitoring modulations of drain current by gate voltage and IV characteristic curves. Due to very thin insulating layers of poly(vinylphenol), the transistors are relative fast under small gate voltage variation although heavy ions are involved in charge transport. In IV characteristic curves, saturation effects can be observed. Analysis using conventional field effect transistor model indicates high mobility of charge carriers, 10 cm2/V·sec, which is not consistent with the mobility of the conducting polymer. It is proposed that the effect of a small density of ions injected via polymer dielectric upon application of gate voltage and the ion compensation of key hopping sites accounts for the operation of the field effect transistors. For the studies of transport under optical field, photovoltaic cells with 3 different dendrons, which are efficient to harvest photo-excited electrons, are used. These dendrons consist of two electron-donors (tetraphenylporphyrin) and one electron-accepter (naphthalenediimide). Steady-state fluorescence measurements show that inter-molecular interaction is dominant in solid dendron film, although intra-molecular interaction is still present. Intra-molecular interaction is suggested by different fluorescence lifetimes between solutions of donor and dendrons. This intra-molecular interaction has two processes, transport via pi-stackings and transport via linking functional groups in the dendrons. IV characteristic spectra of the photovoltaic cells suggest that the transport route of photo-excited charges depends on wavelength of incident light on the cells. For excitation by the Soret band and the lowest Q band, a photo-excited electron can transport directly to a neighbor dendron. For excitation by high-energy Q bands, a photo-excited electron transports via the electron-accepters.

Lincomycin Biosynthesis Involves a Tyrosine Hydroxylating Heme Protein of an Unusual Enzyme Family

PubMed Central

Novotna, Jitka; Olsovska, Jana; Novak, Petr; Mojzes, Peter; Chaloupkova, Radka; Kamenik, Zdenek; Spizek, Jaroslav; Kutejova, Eva; Mareckova, Marketa; Tichy, Pavel; Damborsky, Jiri; Janata, Jiri

2013-01-01

The gene lmbB2 of the lincomycin biosynthetic gene cluster of Streptomyces lincolnensis ATCC 25466 was shown to code for an unusual tyrosine hydroxylating enzyme involved in the biosynthetic pathway of this clinically important antibiotic. LmbB2 was expressed in Escherichia coli, purified near to homogeneity and shown to convert tyrosine to 3,4-dihydroxyphenylalanine (DOPA). In contrast to the well-known tyrosine hydroxylases (EC 1.14.16.2) and tyrosinases (EC 1.14.18.1), LmbB2 was identified as a heme protein. Mass spectrometry and Soret band-excited Raman spectroscopy of LmbB2 showed that LmbB2 contains heme b as prosthetic group. The CO-reduced differential absorption spectra of LmbB2 showed that the coordination of Fe was different from that of cytochrome P450 enzymes. LmbB2 exhibits sequence similarity to Orf13 of the anthramycin biosynthetic gene cluster, which has recently been classified as a heme peroxidase. Tyrosine hydroxylating activity of LmbB2 yielding DOPA in the presence of (6R)-5,6,7,8-tetrahydro-L-biopterin (BH4) was also observed. Reaction mechanism of this unique heme peroxidases family is discussed. Also, tyrosine hydroxylation was confirmed as the first step of the amino acid branch of the lincomycin biosynthesis. PMID:24324587

Modifications of hemoglobin and myoglobin by Maillard reaction products (MRPs).

PubMed

Ioannou, Aristos; Varotsis, Constantinos

2017-01-01

High performance liquid chromatography (HPLC) coupled with a Fraction Collector was employed to isolate Maillard reaction products (MRPs) formed in model systems comprising of asparagine and monosaccharides in the 60-180°C range. The primary MRP which is detected at 60°C is important for Acrylamide content and color/aroma development in foods and also in the field of food biotechnology for controlling the extent of the Maillard reaction with temperature. The discrete fractions of the reaction products were reacted with Hemoglobin (Hb) and Myoglobin (Mb) at physiological conditions and the reaction adducts were monitored by UV-vis and Attenuated Total Reflection-Fourier transform infrared (FTIR) spectrophotometry. The UV-vis kinetic profiles revealed the formation of a Soret transition characteristic of a low-spin six-coordinated species and the ATR-FTIR spectrum of the Hb-MRP and Mb-MRP fractions showed modifications in the protein Amide I and II vibrations. The UV-vis and the FTIR spectra of the Hb-MRPs indicate that the six-coordinated species is a hemichrome in which the distal E7 Histidine is coordinated to the heme Fe and blocks irreversibly the ligand binding site. Although the Mb-MRPs complex is a six-coordinated species, the 1608 cm-1 FTIR band characteristic of a hemichrome was not observed.

Multidetector thermal field-flow fractionation as a unique tool for the tacticity-based separation of poly(methyl methacrylate)-polystyrene block copolymer micelles.

PubMed

Greyling, Guilaume; Pasch, Harald

2015-10-02

Poly(methyl methacrylate)-polystyrene (PMMA-PS) micelles with isotactic and syndiotactic coronas are prepared in acetonitrile and subjected to thermal field-flow fractionation (ThFFF) analysis at various conditions of increasing temperature gradients. It is shown for the first time that multidetector ThFFF provides comprehensive information on important micelle characteristics such as size (Dh), shape (Rg/Rh), aggregation number (Z), thermal diffusion (DT) and Soret coefficients (ST) as a function of temperature from a single injection. Moreover, it is found that micelles exhibit a unique decreasing trend in DT as a function of temperature which is independent of the tacticity of the corona and the micelle preparation method used. It is also demonstrated that ThFFF can monitor micelle to vesicle transitions as a function of temperature. In addition to ThFFF, it is found from DLS analysis that the tacticity of the corona influences the critical micelle concentration and the magnitude to which micelles expand/contract with temperature. The tacticity does not, however, influence the critical micelle temperature. Furthermore, the separation of micelles based on the tacticity of the corona highlight the unique capabilities of ThFFF. Copyright © 2015 Elsevier B.V. All rights reserved.

Analysis of organophosphate-Zn metalloporphyrin interactions via UV-vis spectroscopy and molecular modeling.

PubMed

Rompoti, A; Dalal, N; Athanasopoulos, D; Rutan, S; Helburn, R

2015-01-25

UV-vis absorption spectra of zinc tetraphenylporphine (ZnTPP) on interaction with six organophosphorus (OP) compounds in cyclohexane were compared using ab initio methods and the molecular and solvation ligand descriptors π(*), Vx, and σ. OPs with polarizable hydrocarbon substituents in the homologous series tri-ethyl, -pentyl, -octyl, and -phenyl phosphates and the toxicologically relevant methyl paraoxon (1a-e) each gave a red shift in the Soret band (λsor) of ZnTPP in the range of 8-10 nm. Sensitivity as ΔAsor-b/Δug OP for the spectral band of the ligand bound ZnTPP (λsor-b) decreased with increasing extent of alkyl and aromatic substitution. Calculated and combined energies for OP and ZnTPP examined as a function of distance (Å) between ligand and porphyrin center suggest increased steric crowding with increasing Vx, and aromatic content of the OP. Spectrally fitted K1:1 and ΔAsor-b/ug OP each vary exponentially with Vx/σ. Lack of a red shift in λsor-b where ZnTPP was titrated with the toxic diethyl chlorophosphate (1g) is consistent with a model in which the magnitude of ΔEsor is proportional to the donor capacity of the phosphoryl-O ligand. Copyright © 2014 Elsevier B.V. All rights reserved.

Toward "stable-on-the-table" enzymes: improving key properties of catalase by covalent conjugation with poly(acrylic acid).

PubMed

Riccardi, Caterina M; Cole, Kyle S; Benson, Kyle R; Ward, Jessamyn R; Bassett, Kayla M; Zhang, Yiren; Zore, Omkar V; Stromer, Bobbi; Kasi, Rajeswari M; Kumar, Challa V

2014-08-20

Several key properties of catalase such as thermal stability, resistance to protease degradation, and resistance to ascorbate inhibition were improved, while retaining its structure and activity, by conjugation to poly(acrylic acid) (PAA, Mw 8000) via carbodiimide chemistry where the amine groups on the protein are appended to the carboxyl groups of the polymer. Catalase conjugation was examined at three different pH values (pH 5.0, 6.0, and 7.0) and at three distinct mole ratios (1:100, 1:500, and 1:1000) of catalase to PAA at each reaction pH. The corresponding products are labeled as Cat-PAA(x)-y, where x is the protein to polymer mole ratio and y is the pH used for the synthesis. The coupling reaction consumed about 60-70% of the primary amines on the catalase; all samples were completely water-soluble and formed nanogels, as evidenced by gel electrophoresis and electron microscopy. The UV circular dichroism (CD) spectra indicated substantial retention of protein secondary structure for all samples, which increased to 100% with increasing pH of the synthesis and polymer mole fraction. Soret CD bands of all samples indicated loss of ∼50% of band intensities, independent of the reaction pH. Catalytic activities of the conjugates increased with increasing synthesis pH, where 55-80% and 90-100% activity was retained for all samples synthesized at pH 5.0 and pH 7.0, respectively, and the Km or Vmax values of Cat-PAA(100)-7 did not differ significantly from those of the free enzyme. All conjugates synthesized at pH 7.0 were thermally stable even when heated to ∼85-90 °C, while native catalase denatured between 55 and 65 °C. All conjugates retained 40-90% of their original activities even after storing for 10 weeks at 8 °C, while unmodified catalase lost all of its activity within 2 weeks, under similar storage conditions. Interestingly, PAA surrounding catalase limited access to the enzyme from large molecules like proteases and significantly increased resistance to trypsin digestion compared to unmodified catalase. Similarly, negatively charged PAA surrounding the catalase in these conjugates protected the enzyme against inhibition by negatively charged inhibitors such as ascorbate. While Cat-PAA(100)-7 did not show any inhibition by ascorbate in the presence of 270 μM ascorbate, unmodified catalase lost ∼70% of its activity under similar conditions. This simple, facile, and rational methodology produced thermostable, storable catalase that is also protected from protease digestion and ascorbate inhibition and most likely prevented the dissociation of the multimer. Using synthetic polymers to protect and improve enzyme properties could be an attractive approach for making "Stable-on-the-Table" enzymes, as a viable alternative to protein engineering.

The Negative Testing and Negative Generation Effects Are Eliminated by Delay

ERIC Educational Resources Information Center

Mulligan, Neil W.; Peterson, Daniel J.

2015-01-01

Although retrieval often enhances subsequent memory (the testing effect), a negative testing effect has recently been documented in which prior retrieval harms later recall compared with restudying. The negative testing effect was predicated on the negative generation effect and the item-specific-relational framework. The present experiments…

Sensitivity of negative subsequent memory and task-negative effects to age and associative memory performance.

PubMed

de Chastelaine, Marianne; Mattson, Julia T; Wang, Tracy H; Donley, Brian E; Rugg, Michael D

2015-07-01

The present fMRI experiment employed associative recognition to investigate the relationships between age and encoding-related negative subsequent memory effects and task-negative effects. Young, middle-aged and older adults (total n=136) were scanned while they made relational judgments on visually presented word pairs. In a later memory test, the participants made associative recognition judgments on studied, rearranged (items studied on different trials) and new pairs. Several regions, mostly localized to the default mode network, demonstrated negative subsequent memory effects in an across age-group analysis. All but one of these regions also demonstrated task-negative effects, although there was no correlation between the size of the respective effects. Whereas negative subsequent memory effects demonstrated a graded attenuation with age, task-negative effects declined markedly between the young and the middle-aged group, but showed no further reduction in the older group. Negative subsequent memory effects did not correlate with memory performance within any age group. By contrast, in the older group only, task-negative effects predicted later memory performance. The findings demonstrate that negative subsequent memory and task-negative effects depend on dissociable neural mechanisms and likely reflect distinct cognitive processes. The relationship between task-negative effects and memory performance in the older group might reflect the sensitivity of these effects to variations in amount of age-related neuropathology. This article is part of a Special Issue entitled SI: Memory. Copyright © 2014 Elsevier B.V. All rights reserved.

Good cope, bad cope: adaptive and maladaptive coping strategies following a critical negative work event.

PubMed

Brown, Steven P; Westbrook, Robert A; Challagalla, Goutam

2005-07-01

The authors examined the moderating effects of coping tactics on the relationship between negative emotion and work performance. Findings indicate an adverse effect of emotion on performance; however, this effect is moderated by coping tactics. Venting (expressing one's negative feelings to others) amplified the adverse effects of negative emotion. Self-control had mixed effects: On one hand, it buffered the adverse effects of negative emotion, yet on the other hand, it had a negative direct effect on outcomes. Task focus had a positive direct effect on performance but no buffering (moderating) effect. Implications of these findings for understanding the effects of negative emotion and coping in the workplace are discussed. Copyright 2005 APA, all rights reserved.

Rate and predictors of negative effects of psychotherapy in psychiatric and psychosomatic inpatients.

PubMed

Rheker, Julia; Beisel, Sylvia; Kräling, Svenja; Rief, Winfried

2017-08-01

Studies examining the rates of negative effects of psychotherapy are rare and the reported rates differ widely. To be able to calculate adequate benefit-cost ratios in conjunction with different samples and settings, we need a deeper understanding of these effects. We therefore investigated whether different treatment settings would reveal varying rates and kinds of negative effects by recruiting patients from a psychiatric (n=93) and a psychosomatic rehabilitation (n=63) hospital. Negative effects of psychotherapy were assessed with the Inventory for the Assessment of Negative Effects of Psychotherapy post-treatment. To investigate whether patients' pre-treatment expectations have an influence on reported negative effects, patients filled in the Patient Questionnaire on Therapy Expectation and Evaluation prior to treatment begin. Patients from the psychiatric hospital reported an average 1.41 negative effects, with 58.7% reporting at least one negative effect. Those from the psychosomatic hospital reported 0.76 negative effects on average, with 45.2% of patients reporting at least one negative effect. The differences between these samples are significant. The two samples' top three reported types of negative effects are that patients had experienced more downs during or just before the end of the therapy, that patients had difficulty making important decisions without the therapist, and that patients were concerned that colleagues or friends might find out about the therapy. A regression analysis revealed that the clinical setting (psychosomatic rehabilitation hospital vs. psychiatric hospital) and expectations in the form of hope of improvement were significant predictors for negative effects of psychotherapy. Our study highlights the need to examine the negative effects of psychotherapy in different settings and samples to better evaluate the benefit-cost ratios of treatments for different patient groups. It also shows that we need guidelines for assessing and reporting negative effects. Copyright © 2017 Elsevier Ireland Ltd. All rights reserved.

Is psychotherapy for functional somatic syndromes harmful? A mixed methods study on negative effects.

PubMed

Holsting, A F; Pedersen, H F; Rask, M T; Frostholm, L; Schröder, A

2017-07-01

Concern for negative effects of psychotherapy for functional somatic syndromes (FSS) has been expressed by clinicians and some patient associations, which may prevent patients from seeking treatment. Therefore, we sought to explore the occurrence and characteristics of negative effects from group-based psychotherapy as experienced by patients with severe or multiple FSS. An adapted version of the explanatory sequential mixed methods design was applied. We used data from an on-going pilot study on Acceptance and Commitment Therapy and Mindfulness-Based Stress Reduction. Negative effects were measured by Inventory for the assessment of Negative Effects of Psychotherapy (INEP). In addition, telephone interviews were conducted with randomly chosen patients and patients who reported negative effects. The latter were asked to elaborate on their INEP response. Quantitative data were analysed descriptively while interview transcripts were explored by thematic analysis. Eighty patients responded to the questionnaire (89%). Negative effects to different extent (from 'slightly agree' to 'fully agree') were reported by 25 (31%). The most frequent negative effects were dependence on the therapist (12%), feeling down after therapy (6%) and insurance problems (7%). By exploring 27 participants' experiences of negative effects 3 main themes were identified: relations in therapy, outcome and transition from therapy to everyday life. Patients with FSS reported a few specific negative effects, all with low frequency. Generally, therapy was well-received. Some patients did however express negative effects both within and outside the therapeutic context. It is important to inform patients about potential negative effects prior to psychotherapy. Copyright © 2017 Elsevier Inc. All rights reserved.

Understanding less than nothing: children's neural response to negative numbers shifts across age and accuracy.

PubMed

Gullick, Margaret M; Wolford, George

2013-01-01

We examined the brain activity underlying the development of our understanding of negative numbers, which are amounts lacking direct physical counterparts. Children performed a paired comparison task with positive and negative numbers during an fMRI session. As previously shown in adults, both pre-instruction fifth-graders and post-instruction seventh-graders demonstrated typical behavioral and neural distance effects to negative numbers, where response times and parietal and frontal activity increased as comparison distance decreased. We then determined the factors impacting the distance effect in each age group. Behaviorally, the fifth-grader distance effect for negatives was significantly predicted only by positive comparison accuracy, indicating that children who were generally better at working with numbers were better at comparing negatives. In seventh-graders, negative number comparison accuracy significantly predicted their negative number distance effect, indicating that children who were better at working with negative numbers demonstrated a more typical distance effect. Across children, as age increased, the negative number distance effect increased in the bilateral IPS and decreased frontally, indicating a frontoparietal shift consistent with previous numerical development literature. In contrast, as negative comparison task accuracy increased, the parietal distance effect increased in the left IPS and decreased in the right, possibly indicating a change from an approximate understanding of negatives' values to a more exact, precise representation (particularly supported by the left IPS) with increasing expertise. These shifts separately indicate the effects of increasing maturity generally in numeric processing and specifically in negative number understanding.

Unveiling the water-associated conformational mobility in the active site of ascorbate peroxidase.

PubMed

Chao, Wei-Chih; Lin, Li-Ju; Lu, Jyh-Feng; Wang, Jinn-Shyan; Lin, Tzu-Chieh; Chen, Yi-Han; Chen, Yi-Ting; Yang, Hsiao-Ching; Chou, Pi-Tai

2018-03-01

We carried out comprehensive spectroscopic studies of wild type and mutants of ascorbate peroxidase (APX) to gain understanding of the conformational mobility of the active site. In this approach, three unnatural tryptophans were applied to replace the distal tryptophan (W41) in an aim to probe polarity/water environment near the edge of the heme-containing active site. 7-azatryptophan ((7-aza)Trp) is sensitive to environment polarity, while 2,7-azatryptophan ((2,7-aza)Trp) and 2,6-diazatryptophan ((2,6-aza)Trp) undergo excited-state water-catalyzed double and triple proton transfer, respectively, and are sensitive to the water network. The combination of their absorption, emission bands and the associated relaxation dynamics of these fluorescence probes, together with the Soret-band difference absorption and resonance Raman spectroscopy, lead us to unveil the water associated conformational mobility in the active site of APX. The results are suggestive of the existence of equilibrium between two different environments surrounding W41 in APX, i.e., the water-rich and water-scant forms with distinct fluorescence relaxation. Our results thus demonstrate for the first time the power of integrating multiple sensors (7-aza)Trp, (2,7-aza)Trp and (2,6-aza)Trp in probing the water environment of a specifically targeted Trp in proteins. Copyright © 2017 Elsevier B.V. All rights reserved.

Student Outreach with Renewable Energy Technology

NASA Technical Reports Server (NTRS)

Buffinger, D. R.; Fuller, C. W.; Gordon, E. M.; Kalu, A.; Hepp, Aloysius F. (Technical Monitor)

2000-01-01

The Student Outreach with Renewable Energy Technology (SORET) program is an education program involving three Historically Black Colleges and Universities and NASA's John H. Glenn Research Center at Lewis Field. These three universities; Central State University (CSU), Savannah State University (SSU) and Wilberforce University (WU) are working together with NASA Glenn to use the theme of renewable energy to improve the science, engineering and technology education of minority students and to attract minority students to these fields. In this vein, a renewable energy laboratory course is being offered at WU with the goal of giving the students of WU and CSU hands on experiences. As part of this course, the students are constructing solar light posts for a local high school with a high minority population. A Physics teacher from this school and some of his high school students are involved with this project. A lecture course on energy systems and sustainability is being developed by SSU to be delivered via distance reaming to the other institutions. Summer activities are being planned at all three institutions involving student projects in renewable energy. For example, WU students will work on a study of the synthesis and properties of photovoltaic materials. In addition, CSU will present a weeklong summer program to high school students with the assistance of WU. This presentation will focus on the student involvement and achievements in the educational area to date and plot the future course of this program.

Spectroscopic investigation of light-induced intracellular reactions of hydrophilic meso-tetraphenylporphyrins

NASA Astrophysics Data System (ADS)

Rueck, Angelika C.; Strauss, Wolfgang S. L.; Schneckenburger, Herbert; Steiner, Rudolf W.

1992-06-01

Light-induced reactions of different hydrophilic meso-tetraphenyl porphyrins (TPPS4, TPPC4, T4MPyP) were investigated during PDT treatment. These measurements were carried out in vitro using micro-spectrofluorometry and were correlated with measurements in buffer solutions. In the case of the anionic TPPS4, before light exposure, a neutral free base and a protonated species could be detected simultaneously in the cells. During irradiation, the protonated species first disappeared. Due to the fact that a coexistence of a protonated and unprotonated species requires a pH value around 5, TPPS4 was at first located in the lysosomes (pH 5) and was released into the cytoplasm during irradiation as a result of lysosomal rupture. Further light exposure led to a drastic fluorescence formation in the nuclei, in particular the nucleoli of the cells, which was concomitant with a renewed observation of a fluorescence emission spectrum similar to that of the protonated species. In the case of the anionic TPPC4, a similar fluorescence increase was observed during irradiation. However, the formation of a protonated species played a less important role. The cationic T4MPyP again showed fluorescence increase during irradiation. Two Soret-bands separated by about 20 nm could be detected. The red-shifted band may be due to a special intercalation of T4MPyP in nucleic acids.

Method for the quantification of vanadyl porphyrins in fractions of crude oils by High Performance Liquid Chromatography-Flow Injection-Inductively Coupled Plasma Mass Spectrometry

NASA Astrophysics Data System (ADS)

Wandekoken, Flávia G.; Duyck, Christiane B.; Fonseca, Teresa C. O.; Saint'Pierre, Tatiana D.

2016-05-01

High performance liquid chromatography hyphenated by flow injection to inductively coupled plasma mass spectrometry (HPLC-FI-ICP-MS) was used to investigate V linked to porphyrins present in fractions of crude oil. First, the crude oil sample was submitted to fractionation by preparative liquid chromatography with UV detection, at the porphyrin Soret band wavelength (400 nm). The obtained porphyrin fractions were then separated in a 250 mm single column, in the HPLC, and eluted with different mobile phases (methanol or methanol:toluene (80:20; v:v)). The quantification of V-porphyrins in the fractions eluted from HPLC was carried out by online measuring the 51V isotope in the ICP-MS, against vanadyl octaethylporphine standard solutions (VO-OEP), prepared in the same solvent as the mobile phase, and injected post-column directly into the plasma. A 20 μg L- 1 Ge in methanol was used as internal standard for minimizing non-spectral interference, such as short-term variations due to injection. The mathematical treatment of the signal based on Fast Fourier Transform smoothing algorithm was employed to improve the precision. The concentrations of V as V-porphyrins were between 2.7 and 11 mg kg- 1 in the fractions, which were close to the total concentration of V in the porphyrin fractions of the studied crude oil.

Spectroscopic, Structural, and Functional Characterization of the Alternative Low-Spin State of Horse Heart Cytochrome c

PubMed Central

Mugnol, Katia C. U.; Ando, Rômulo A.; Nagayasu, Rafael Y.; Faljoni-Alario, Adelaide; Brochsztain, Sergio; Santos, Paulo S.; Nascimento, Otaciro R.; Nantes, Iseli L.

2008-01-01

The alternative low-spin states of Fe3+ and Fe2+ cytochrome c induced by SDS or AOT/hexane reverse micelles exhibited the heme group in a less rhombic symmetry and were characterized by electron paramagnetic resonance, UV-visible, CD, magnetic CD, fluorescence, and Raman resonance. Consistent with the replacement of Met80 by another strong field ligand at the sixth heme iron coordination position, Fe3+ ALSScytc exhibited 1-nm Soret band blue shift and ɛ enhancement accompanied by disappearance of the 695-nm charge transfer band. The Raman resonance, CD, and magnetic CD spectra of Fe3+ and Fe2+ ALSScytc exhibited significant changes suggestive of alterations in the heme iron microenvironment and conformation and should not be assigned to unfold because the Trp59 fluorescence remained quenched by the neighboring heme group. ALSScytc was obtained with His33 and His26 carboxyethoxylated horse cytochrome c and with tuna cytochrome c (His33 replaced by Asn) pointing out Lys79 as the probable heme iron ligand. Fe3+ ALSScytc retained the capacity to cleave tert-butylhydroperoxide and to be reduced by dithiothreitol and diphenylacetaldehyde but not by ascorbate. Compatible with a more open heme crevice, ALSScytc exhibited a redox potential ∼200 mV lower than the wild-type protein (+220 mV) and was more susceptible to the attack of free radicals. PMID:18227133

Synthesis, characterization, and nonlinear optical properties of graphene oxide functionalized with tetra-amino porphyrin

NASA Astrophysics Data System (ADS)

Yamuna, R.; Ramakrishnan, S.; Dhara, Keerthy; Devi, R.; Kothurkar, Nikhil K.; Kirubha, E.; Palanisamy, P. K.

2013-01-01

The synthesis of a porphyrin-graphene oxide hybrid (GO-TAP) was carried out by covalently functionalizing graphene oxide (GO) with 5,10,15,20 mesotetra (4-aminophenyl) porphyrin (TAP) through an amide linkage. The GO-TAP hybrid has been characterized by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and UV-visible spectroscopy. The peak intensity of the Soret band of the material was suppressed compared to neat TAP. This indicates a strong interaction between the electronic energy level of TAP and GO in the GO-TAP hybrid. The functionalization of GO with TAP significantly improved its solubility and dispersion stability in organic solvents. Scanning electron micrographs reveal that the hybrid was found to be similar to the unmodified GO but slightly more wrinkled. Transmission electron micrographs also demonstrate that GO sheet in the hybrid is more wrinkled with some dark spot due to functionalization. Atomic force microscopy results also reveal that the TAP functionalization increases the thickness of GO sheet to 2.0-3.0 nm from 1.2 to 1.8 nm. We observed improved nonlinear optical and optical limiting properties for the hybrid compared to both graphene oxide and porphyrin. GO-TAP shows fluorescence quenching compared with porphyrin, indicating excellent electron and/or energy transfer to GO from TAP. Thermogravimetric analysis confirms that the GO-TAP hybrid has outstanding thermal stability.

Thermal diffusion forced Rayleigh scattering setup optimized for aqueous mixtures.

PubMed

Wiegand, Simone; Ning, Hui; Kriegs, Hartmut

2007-12-27

We developed a thermal diffusion forced Rayleigh scattering (TDFRS) setup operating at a writing wavelength of 980 nm, which corresponds to an absorption band of water with an absorption coefficient of approximately 0.5 cm(-1). Therefore, aqueous mixtures require no dye to convert the light into heat energy. Especially for aqueous system with a complex phase behavior such as surfactant systems, the addition of a water soluble dye can cause artifacts. The infrared-TDFRS (IR-TDFRS) setup has been validated for water/ethanol mixtures with water weight fractions c = 0.5-0.95 and in a temperature range between T = 15 degrees C to T = 35 degrees C. Comparison with literature data shows an excellent agreement. The addition of a small amount (c(dye) approximately 10(-6) wt) of adsorbing dye at the writing wavelength allows also the investigation of organic mixtures. We investigated the three binary mixtures of dodecane, isobutylbenzene, and 1,2,3,4-tetrahydronaphthalene at a weight fraction of c = 0.5 at a temperature of 25 degrees C and found good agreement with the Soret coefficients, which had been obtained in a benchmark test under the same conditions. Therefore, the presented setup is suitable for the investigation of the thermal diffusion behavior in aqueous and organic mixtures, and in the case of aqueous systems, the addition of a dye can be avoided.

Multidetector thermal field-flow fractionation as a novel tool for the microstructure separation of polyisoprene and polybutadiene.

PubMed

Greyling, Guilaume; Pasch, Harald

2014-11-01

For the first time, it is demonstrated that thermal field-flow fractionation (ThFFF) is an efficient tool for the fractionation of polyisoprene (PI) and polybutadiene (PB) with regard to molecular microstructure. ThFFF analysis of 1,4- and 3,4-PI as well as 1,4- and 1,2-PB samples in tetrahydrofuran (THF), THF/cyclohexane, and cyclohexane reveals that isomers of the same polymer family having similar molar masses exhibit different Soret coefficients depending on microstructure for each solvent. The separation according to microstructure is found to be based on the cooperative influence of the normal and the thermal diffusion coefficient. Of the three solvents, cyclohexane has the greatest influence on the fractionation of the isomers. In order to determine the distribution of isomeric structures in the PI and PB samples, the samples are fractionated by ThFFF in cyclohexane and subsequently analyzed by (1) H NMR. The isomeric distributions determined from NMR data correlate well with ThFFF retention data of the samples and thus further highlight the unique fractionating capabilities of ThFFF. The interplay of the normal and thermal diffusion coefficients that are influenced by temperature and the mobile phase opens the way to highly selective fractionations without the drawbacks of column-based separation methods. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Formation of a bioconjugate composed of hemin, smectite, and quaternary ammonium chloride that is soluble and active in hydrophobic media.

PubMed

Kurosawa, Masaru; Itoh, Tetsuji; Kodera, Yoh; Matsushima, Ayako; Hiroto, Misao; Nishimura, Hiroyuki; Inada, Yuji

2002-01-01

Hemin (Fe(3+)) was adsorbed onto synthetic smectite (clay mineral) intercalated with a quaternary alkenylammonium compound, dioleyldimethylammonium chloride (DOA), to form a hemin-smectite-DOA conjugate. The hemin-smectite-DOA conjugate was soluble in organic solvents such as benzene and toluene to form a transparent colloidal solution with a light yellow color. Its absorption spectrum in benzene showed two bands, 600 and 568 nm, in the visible region and a sharp Soret band at 400 nm with the molar extinction coefficient of 7.5 x 10(4) M(-1) cm(-1). The formation of the conjugate of smectite and DOA was confirmed by X-ray diffraction analysis: the basal spacing, d(001), of hemin-smectite-DOA conjugate was 19 A which is an expansion of the interlayer space by 5 A based upon the basal spacing of smectite of 14 A. Hemin-smectite-DOA conjugate catalyzed the peroxidase-like reaction in organic solvents using benzoyl peroxide as the hydrogen acceptor and leucocrystal violet as the hydrogen donor. The temperature-dependent peroxidase-like activity of the conjugate was compared with peroxidase activity of horseradish peroxidase. The hemin-smectite-DOA conjugate exhibited higher activity as the temperature was increased from 30 to 70 degrees C, while horseradish peroxidase activity was reduced as the temperature was increased.

Two-Photon Absorbing Phosphorescent Metalloporphyrins: Effects of π-Extension and Peripheral Substitution.

PubMed

Esipova, Tatiana V; Rivera-Jacquez, Héctor J; Weber, Bruno; Masunov, Artëm E; Vinogradov, Sergei A

2016-12-07

The ability to form triplet excited states upon two-photon excitation is important for several applications of metalloporphyrins, including two-photon phosphorescence lifetime microscopy (2PLM) and two-photon photodynamic therapy (PDT). Here we analyzed one-photon (1P) and degenerate two-photon (2P) absorption properties of several phosphorescent Pt (II) porphyrins, focusing on the effects of aromatic π-extension and peripheral substitution on triplet emissivity and two-photon absorption (2PA). Our 2PA measurements for the first time made use of direct time-resolved detection of phosphorescence, having the ability to efficiently reject laser background through microsecond time gating. π-Extension of the porphyrin macrocycle by way of syn-fusion with two external aromatic fragments, such as in syn-dibenzo- (DBP) and syn-dinaphthoporphyrins (DNP), lowers the symmetry of the porphyrin skeleton. As a result, DBPs and DNPs exhibit stronger 2PA into the one-photon-allowed B (Soret) and Q states than fully symmetric (D 4h ) nonextended porphyrins. However, much more 2P-active states lie above the B state and cannot be accessed due to the interfering linear absorption. Alkoxycarbonyl groups (CO 2 R) in the benzo-rings dramatically enhance 2PA near the B state level. Time-dependent density functional theory (TDDFT) calculations in combinations with the sum-over-states (SOS) formalism revealed that the enhancement is due to the stabilization of higher-lying 2P-active states, which are dominated by the excitations involving orbitals extending onto the carbonyl groups. Furthermore, calculations predicted even stronger stabilization of the 2P-allowed gerade-states in symmetric Pt octaalkoxycarbonyl-tetrabenzoporphyrins. Experiments confirmed that the 2PA cross-section of PtTBP(CO 2 Bu) 8 near 810 nm reaches above 500 GM in spite of its completely centrosymmetric structure. Combined with exceptionally bright phosphorescence (ϕ phos = 0.45), strong 2PA makes Pt(II) complexes of π-extended porphyrins a valuable class of chromophores for 2P applications. Another important advantage of these porphyrinoids is their compact size and easily scalable synthesis.

Tetra-2,3-pyrazinoporphyrazines with externally appended pyridine rings. 15. Effects of the pyridyl substituents and fused exocyclic rings on the UV-visible spectroscopic properties of Mg(II)-porphyrazines: a combined experimental and DFT/TDDFT study.

PubMed

Donzello, Maria Pia; De Mori, Giorgia; Viola, Elisa; Ercolani, Claudio; Ricciardi, Giampaolo; Rosa, Angela

2014-08-04

Two new Mg(II) porphyrazine macrocycles, the octakis(2-pyridyl)porphyrazinato-magnesium(II), [Py8PzMg(H2O)], and the tetrakis-[6,7-di(2-pyridyl)quinoxalino]porphyrazinato-magnesium(II), [Py8QxPzMg(H2O)], were prepared by Mg-template macrocyclization processes, and their general physicochemical properties were examined. The previously reported porphyrazine analog, the tetrakis-2,3-[5,6-di(2-pyridyl)-pyrazino]porphyrazinato-magnesium(II), [Py8PyzPzMg(H2O)], has been also considered in the present work. The UV-visible solution spectra in nonaqueous solvents of this triad of externally octapyridinated Mg(II) complexes exhibit the usual profile observed for phthalocyanine and porphyrazine macrocycles, with intense absorptions in the Soret (300-450 nm) and Q band (600-800 nm) regions. It is observed that the Q band maximum sensibly shifts toward the red with peak values at 635 → 658 → 759 nm along the series [Py8PzMg(H2O)], [Py8PyzPzMg(H2O)], and [Py8QxPzMg(H2O)], as the extension of the macrocycle π-system increases. TDDFT calculations of the electronic absorption spectra were performed for the related water-free model compounds [Py8PzMg], [Py8PyzPzMg], and [Py8QxPzMg] to provide an interpretation of the UV-visible spectral changes occurring upon introduction of the pyrazine and quinoxaline rings at the periphery of the Pz macrocycle. To discriminate the electronic effects of the fused exocyclic rings from those of the appended 2-pyridyl rings, the UV-visible spectra of [PzMg] and [PyzPzMg] were also theoretically investigated. The theoretical results prove to agree very well with the experimental data, providing an accurate description of the UV-visible spectra. The observed spectral changes are interpreted on the basis of the electronic structure changes occurring along the series.

Potential negative ecological effects of corridors.

PubMed

Haddad, Nick M; Brudvig, Lars A; Damschen, Ellen I; Evans, Daniel M; Johnson, Brenda L; Levey, Douglas J; Orrock, John L; Resasco, Julian; Sullivan, Lauren L; Tewksbury, Josh J; Wagner, Stephanie A; Weldon, Aimee J

2014-10-01

Despite many studies showing that landscape corridors increase dispersal and species richness for disparate taxa, concerns persist that corridors can have unintended negative effects. In particular, some of the same mechanisms that underlie positive effects of corridors on species of conservation interest may also increase the spread and impact of antagonistic species (e.g., predators and pathogens), foster negative effects of edges, increase invasion by exotic species, increase the spread of unwanted disturbances such as fire, or increase population synchrony and thus reduce persistence. We conducted a literature review and meta-analysis to evaluate the prevalence of each of these negative effects. We found no evidence that corridors increase unwanted disturbance or non-native species invasion; however, these have not been well-studied concerns (1 and 6 studies, respectively). Other effects of corridors were more often studied and yielded inconsistent results; mean effect sizes were indistinguishable from zero. The effect of edges on abundances of target species was as likely to be positive as negative. Corridors were as likely to have no effect on antagonists or population synchrony as they were to increase those negative effects. We found 3 deficiencies in the literature. First, despite studies on how corridors affect predators, there are few studies of related consequences for prey population size and persistence. Second, properly designed studies of negative corridor effects are needed in natural corridors at scales larger than those achievable in experimental systems. Third, studies are needed to test more targeted hypotheses about when corridor-mediated effects on invasive species or disturbance may be negative for species of management concern. Overall, we found no overarching support for concerns that construction and maintenance of habitat corridors may result in unintended negative consequences. Negative edge effects may be mitigated by widening corridors or softening edges between corridors and the matrix. Other negative effects are relatively small and manageable compared with the large positive effects of facilitating dispersal and increasing diversity of native species. © 2014 Society for Conservation Biology.

Religious Engagement in a Risky Family Model Predicting Health in Older Black and White Seventh-day Adventists.

PubMed

Morton, Kelly R; Lee, Jerry W; Haviland, Mark G; Fraser, Gary E

2012-11-01

In a structural equation model, associations among latent variables - Child Poverty, Risky Family exposure, Religious Engagement, Negative Social Interactions, Negative Emotionality, and Perceived Physical Health - were evaluated in 6,753 Black and White adults aged 35-106 years (M = 60.5, SD = 13.0). All participants were members of the Seventh-day Adventist church surveyed in the Biopsychosocial Religion and Health Study (BRHS). Child Poverty was positively associated with both Risky Family exposure (conflict, neglect, abuse) and Religious Engagement (intrinsic religiosity, religious coping, religiousness). Risky Family was negatively associated with Religious Engagement and positively associated with both Negative Social Interactions (intrusive, failed to help, insensitive, rejecting) and Negative Emotionality (depression, negative affect, neuroticism). Religious Engagement was negatively associated with Negative Emotionality and Negative Social Interactions at a given level of risky family. Negative Social Interactions was positively associated with Negative Emotionality, which had a direct, negative effect on Perceived Physical Health. All constructs had indirect effects on Perceived Physical Health through Negative Emotionality. The effects of a risky family environment appear to be enduring, negatively affecting one's adult religious life, emotionality, social interactions, and perceived health. Religious engagement, however, may counteract the damaging effects of early life stress.

Expression and purification of spinach nitrite reductase in E. coli

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

Bellissimo, D.; Privalle, L.

1991-03-11

The study of structure-function relationships in nitrite reductase (NiR) by site-directed mutagenesis requires an expression system from which suitable quantities of active enzyme can be purified. Spinach NiR cDNA was cloned into pUC18 and expressed in E.coli JM109 as a beta-galactosidase fusion protein. The IPTG-induced fusion protein contains five additional amino acids at the N-terminus. The expressed NiR in aerobic cultures was mostly insoluble and inactive indicating the presence of inclusion bodies. By altering growth conditions, active NiR could represent 0.5-1.0% of the total E.coli protein, Effects of the addition of delta-aminolevulinic acid, a heme precursor, and anaerobic growth weremore » also examined. Spinach NiR was purified approximately 200 fold to homogeneity. When subjected to electrophoresis on SDS polyacrylamide gels, the NiR migrated as a single band with similar mobility to pure spinach enzyme. The expressed enzyme also reacted with rabbit anti-spinach NiR antibody as visualized by Western blot analysis. The absorption spectrum of the E.coli-expressed enzyme was identical to spinach enzyme with a Soret and alpha band a 386 and 573 nm, respectively, and an A{sub 278}/A{sub 386} = 1.9. The addition of nitrite produced the characteristic shifts in the spectrum. The E. coli-expressed NiR catalyzed the methylviologen-dependent reduction of nitrite. The specific activity was 100 U/mg. The K{sub m} determined for nitrite was 0.3 mM which is in agreement with values reported for the enzyme. These results indicate that the E.coli-expressed NiR is fully comparable to spinach NiR in purity, catalytic activity and physical state. Site-directed mutants have been made using PCR to examine structure-function relationships in this enzyme.« less

Insights into signal transduction by a hybrid FixL: Denaturation study of on and off states of a multi-domain oxygen sensor.

PubMed

Guimarães, Wellinson G; Gondim, Ana C S; Costa, Pedro Mikael da Silva; Gilles-Gonzalez, Marie-Alda; Lopes, Luiz G F; Carepo, Marta S P; Sousa, Eduardo H S

2017-07-01

FixL from Rhizobium etli (ReFixL) is a hybrid oxygen sensor protein. Signal transduction in ReFixL is effected by a switch off of the kinase activity on binding of an oxygen molecule to ferrous heme iron in another domain. Cyanide can also inhibit the kinase activity upon binding to the heme iron in the ferric state. The unfolding by urea of the purified full-length ReFixL in both active pentacoordinate form, met-FixL(Fe III ) and inactive cyanomet-FixL (Fe III -CN - ) form was monitored by UV-visible absorption spectroscopy, circular dichroism (CD) and fluorescence spectroscopy. The CD and UV-visible absorption spectroscopy revealed two states during unfolding, whereas fluorescence spectroscopy identified a three-state unfolding mechanism. The unfolding mechanism was not altered for the active compared to the inactive state; however, differences in the ΔG H2O were observed. According to the CD results, compared to cyanomet-FixL, met-FixL was more stable towards chemical denaturation by urea (7.2 vs 4.8kJmol -1 ). By contrast, electronic spectroscopy monitoring of the Soret band showed cyanomet-FixL to be more stable than met-FixL (18.5 versus 36.2kJmol -1 ). For the three-state mechanism exhibited by fluorescence, the ΔG H2O for both denaturation steps were higher for the active-state met-FixL than for cyanomet-FixL. The overall stability of met-FixL is higher in comparison to cyanomet-FixL suggesting a more compact protein in the active form. Nonetheless, hydrogen bonding by bound cyanide in the inactive state promotes the stability of the heme domain. This work supports a model of signal transduction by FixL that is likely shared by other heme-based sensors. Copyright © 2017 Elsevier Inc. All rights reserved.

Ligand Noninnocence in Iron Corroles: Insights from Optical and X-ray Absorption Spectroscopies and Electrochemical Redox Potentials

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

Ganguly, Sumit; Giles, Logan J.; Thomas, Kolle E.

Two new series of iron meso-tris(para-X-phenyl)corrole (TpXPC) complexes, Fe[TpXPC]Ph and Fe[TpXPC]Tol, in which X=CF 3, H, Me, and OMe, and Tol=p-methylphenyl (p-tolyl), have been synthesized, allowing a multitechnique electronic–structural comparison with the corresponding FeCl, FeNO, and Fe 2(μ-O) TpXPC derivatives. Optical spectroscopy revealed that the Soret maxima of the FePh and FeTol series are insensitive to the phenyl para substituent, consistent with the presumed innocence of the corrole ligand in these compounds. Accordingly, we may be increasingly confident in the ability of the substituent effect criterion to serve as a probe of corrole noninnocence. Furthermore, four complexes—Fe[TPC]Cl, Fe[TPC](NO), {Fe[TPC]} 2O,more » and Fe[TPC]Ph—were selected for a detailed XANES investigation of the question of ligand noninnocence. The intensity-weighted average energy (IWAE) positions were found to exhibit rather modest variations (0.8 eV over the series of corroles). The integrated Fe-K pre-edge intensities, on the other hand, vary considerably, with a 2.5 fold increase for Fe[TPC]Ph relative to Fe[TPC]Cl and Fe[TPC](NO). Given the approximately C 4v local symmetry of the Fe in all the complexes, the large increase in intensity for Fe[TPC]Ph may be attributed to a higher number of 3d holes, consistent with an expected Fe IV-like description, in contrast to Fe[TPC]Cl and Fe[TPC](NO), in which the Fe is thought to be Fe III-like. In conclusion, these results afford strong validation of XANES as a probe of ligand noninnocence in metallocorroles. Electrochemical redox potentials, on the other hand, were found not to afford a simple probe of ligand noninnocence in Fe corroles.« less

Ligand Noninnocence in Iron Corroles: Insights from Optical and X-ray Absorption Spectroscopies and Electrochemical Redox Potentials

DOE PAGES

Ganguly, Sumit; Giles, Logan J.; Thomas, Kolle E.; ...

2017-10-06

Two new series of iron meso-tris(para-X-phenyl)corrole (TpXPC) complexes, Fe[TpXPC]Ph and Fe[TpXPC]Tol, in which X=CF 3, H, Me, and OMe, and Tol=p-methylphenyl (p-tolyl), have been synthesized, allowing a multitechnique electronic–structural comparison with the corresponding FeCl, FeNO, and Fe 2(μ-O) TpXPC derivatives. Optical spectroscopy revealed that the Soret maxima of the FePh and FeTol series are insensitive to the phenyl para substituent, consistent with the presumed innocence of the corrole ligand in these compounds. Accordingly, we may be increasingly confident in the ability of the substituent effect criterion to serve as a probe of corrole noninnocence. Furthermore, four complexes—Fe[TPC]Cl, Fe[TPC](NO), {Fe[TPC]} 2O,more » and Fe[TPC]Ph—were selected for a detailed XANES investigation of the question of ligand noninnocence. The intensity-weighted average energy (IWAE) positions were found to exhibit rather modest variations (0.8 eV over the series of corroles). The integrated Fe-K pre-edge intensities, on the other hand, vary considerably, with a 2.5 fold increase for Fe[TPC]Ph relative to Fe[TPC]Cl and Fe[TPC](NO). Given the approximately C 4v local symmetry of the Fe in all the complexes, the large increase in intensity for Fe[TPC]Ph may be attributed to a higher number of 3d holes, consistent with an expected Fe IV-like description, in contrast to Fe[TPC]Cl and Fe[TPC](NO), in which the Fe is thought to be Fe III-like. In conclusion, these results afford strong validation of XANES as a probe of ligand noninnocence in metallocorroles. Electrochemical redox potentials, on the other hand, were found not to afford a simple probe of ligand noninnocence in Fe corroles.« less

Influence of convection on microstructure

NASA Technical Reports Server (NTRS)

Wilcox, William R.; Regel, Liya L.

1994-01-01

The primary motivation for this research was to determine the cause for space processing altering the microstructure of some eutectics, especially the MnBi-Bi eutectic. Four primary hypotheses were to be tested under this current grant: (1) A fibrous microstructure is much more sensitive to convection than a lamellar microstructure, which was assumed in our prior theoretical treatment. (2) An interface with one phase projecting out into the melt is much more sensitive to convection than a planar interface, which was assumed in our prior theoretical treatment. (3) The Soret effect is much more important in the absence of convection and has a sufficiently large influence on microstructure that its action can explain the flight results. (4) The microstructure is much more sensitive to convection when the composition of the bulk melt is off eutectic. These hypotheses were tested. It was concluded that none of these can explain the Grumman flight results. Experiments also were performed on the influence of current pulses on MnBi-Bi microstructure. A thorough review was made of all experimental results on the influence of convection on the fiber spacing in rod eutectics, including results from solidification in space or at high gravity, and use of mechanical stirring or a magnetic field. Contradictory results were noted. The predictions of models for convective influences were compared with the experimental results. Vigorous mechanical stirring appears to coarsen the microstructure by altering the concentration field in front of the freezing interface. Gentle convection is believed to alter the microstructure of a fibrous eutectic only when it causes a fluctuating freezing rate with a system for which the kinetics of fiber branching differs from that for fiber termination. These fluctuations may cause the microstructure to coarsen or to become finer, depending on the relative kinetics of these processes. The microstructure of lamellar eutectics is less sensitive to freezing rate fluctuations and to gentle convection.

Planning what not to eat: ironic effects of implementation intentions negating unhealthy habits.

PubMed

Adriaanse, Marieke A; van Oosten, Johanna M F; de Ridder, Denise T D; de Wit, John B F; Evers, Catharine

2011-01-01

The present studies tested the effectiveness of implementation intentions with an "if [situation], then not [habitual response]" structure. Based on ironic process theory and the literature on the processing of negations, it was expected that these "negation implementation intentions" would, ironically, strengthen the habit (situation-response association) one aims to break. In line with the hypotheses, forming negation implementation intentions resulted in cognitive ironic rebound effects as well as behavioral ironic rebound effects compared to an intention only condition or a replacement implementation intention. Additionally, it was found that negation implementation intentions are most likely to result in ironic rebound effects when the habit to be negated is strong. Although implementation intentions are generally highly effective in facilitating behavior change even when this involves breaking unwanted habits, the present research suggests that they are ineffective when they have a negating structure.

The indirect effect of emotion dysregulation in terms of negative affect and smoking-related cognitive processes.

PubMed

Johnson, Adrienne L; McLeish, Alison C

2016-02-01

Although negative affect is associated with a number of smoking-related cognitive processes, the mechanisms underlying these associations have yet to be examined. The current study sought to examine the indirect effect of emotion regulation difficulties in terms of the association between negative affect and smoking-related cognitive processes (internal barriers to cessation, negative affect reduction smoking motives, negative affect reduction smoking outcome expectancies). Participants were 126 daily cigarette smokers (70.4% male, Mage=36.5years, SD=13.0; 69.8% Caucasian) who smoked an average of 18.5 (SD=8.7) cigarettes per day and reported moderate nicotine dependence. Formal mediation analyses were conducted using PROCESS to examine the indirect effect of negative affect on internal barriers to cessation and negative affect reduction smoking motives and outcome expectancies through emotion regulation difficulties. After accounting for the effects of gender, daily smoking rate, and anxiety sensitivity, negative affect was indirectly related to internal barriers to cessation and negative affect reduction smoking motives through emotion regulation difficulties. There was no significant indirect effect for negative affect reduction smoking outcome expectancies. These findings suggest that greater negative affect is associated with a desire to smoke to reduce this negative affect and perceptions that quitting smoking will be difficult due to negative emotions because of greater difficulties managing these negative emotions. Thus, emotion regulation difficulties may be an important target for smoking cessation interventions. Copyright © 2015 Elsevier Ltd. All rights reserved.

Religious Engagement in a Risky Family Model Predicting Health in Older Black and White Seventh-day Adventists

PubMed Central

Morton, Kelly R.; Lee, Jerry W.; Haviland, Mark G.; Fraser, Gary E.

2012-01-01

In a structural equation model, associations among latent variables – Child Poverty, Risky Family exposure, Religious Engagement, Negative Social Interactions, Negative Emotionality, and Perceived Physical Health – were evaluated in 6,753 Black and White adults aged 35–106 years (M = 60.5, SD = 13.0). All participants were members of the Seventh-day Adventist church surveyed in the Biopsychosocial Religion and Health Study (BRHS). Child Poverty was positively associated with both Risky Family exposure (conflict, neglect, abuse) and Religious Engagement (intrinsic religiosity, religious coping, religiousness). Risky Family was negatively associated with Religious Engagement and positively associated with both Negative Social Interactions (intrusive, failed to help, insensitive, rejecting) and Negative Emotionality (depression, negative affect, neuroticism). Religious Engagement was negatively associated with Negative Emotionality and Negative Social Interactions at a given level of risky family. Negative Social Interactions was positively associated with Negative Emotionality, which had a direct, negative effect on Perceived Physical Health. All constructs had indirect effects on Perceived Physical Health through Negative Emotionality. The effects of a risky family environment appear to be enduring, negatively affecting one’s adult religious life, emotionality, social interactions, and perceived health. Religious engagement, however, may counteract the damaging effects of early life stress. PMID:23560134

Negative affect, negative urgency, thought suppression, and bulimic symptoms: a moderated mediation analysis in a sample at-risk for bulimic symptoms.

PubMed

Lavender, Jason M; Green, Daniel; Anestis, Michael D; Tull, Matthew T; Gratz, Kim L

2015-05-01

Research suggests that negative affect, negative urgency, and thought suppression are related to bulimic symptoms, either directly or indirectly. This study examined associations between these constructs in a sample at-risk for bulimic symptoms. Participants (N = 80) recruited from a residential substance abuse treatment facility completed self-report questionnaires. A regression-based bootstrapping approach was used to examine the indirect effect of negative affect on bulimic symptoms through negative urgency and the moderating role of thought suppression in the association between negative affect and negative urgency. Results revealed a significant indirect effect, significant moderation, and a significant moderated mediation effect, with an indirect effect of negative affect on bulimic symptoms through negative urgency, conditional upon low to moderate (but not high) levels of thought suppression. These findings suggest that negative affect may promote rash actions, particularly in the context of low to moderate thought suppression, leading to increased risk of bulimic symptoms. Copyright © 2015 John Wiley & Sons, Ltd and Eating Disorders Association.

Brand Suicide? Memory and Liking of Negative Brand Names

PubMed Central

Guest, Duncan; Estes, Zachary; Gibbert, Michael; Mazursky, David

2016-01-01

Negative brand names are surprisingly common in the marketplace (e.g., Poison perfume; Hell pizza, and Monster energy drink), yet their effects on consumer behavior are currently unknown. Three studies investigated the effects of negative brand name valence on brand name memory and liking of a branded product. Study 1 demonstrates that relative to non-negative brand names, negative brand names and their associated logos are better recognised. Studies 2 and 3 demonstrate that negative valence of a brand name tends to have a detrimental influence on product evaluation with evaluations worsening as negative valence increases. However, evaluation is also dependent on brand name arousal, with high arousal brand names resulting in more positive evaluations, such that moderately negative brand names are equally as attractive as some non-negative brand names. Study 3 shows evidence for affective habituation, whereby the effects of negative valence reduce with repeated exposures to some classes of negative brand name. PMID:27023872

Brand Suicide? Memory and Liking of Negative Brand Names.

PubMed

Guest, Duncan; Estes, Zachary; Gibbert, Michael; Mazursky, David

2016-01-01

Negative brand names are surprisingly common in the marketplace (e.g., Poison perfume; Hell pizza, and Monster energy drink), yet their effects on consumer behavior are currently unknown. Three studies investigated the effects of negative brand name valence on brand name memory and liking of a branded product. Study 1 demonstrates that relative to non-negative brand names, negative brand names and their associated logos are better recognised. Studies 2 and 3 demonstrate that negative valence of a brand name tends to have a detrimental influence on product evaluation with evaluations worsening as negative valence increases. However, evaluation is also dependent on brand name arousal, with high arousal brand names resulting in more positive evaluations, such that moderately negative brand names are equally as attractive as some non-negative brand names. Study 3 shows evidence for affective habituation, whereby the effects of negative valence reduce with repeated exposures to some classes of negative brand name.

Turning negative into positive: public health mass media campaigns and negative advertising.

PubMed

Apollonio, D E; Malone, R E

2009-06-01

Literature suggests that 'negative advertising' is an effective way to encourage behavioral changes, but it has enjoyed limited use in public health media campaigns. However, as public health increasingly focuses on non-communicable disease prevention, negative advertising could be more widely applied. This analysis considers an illustrative case from tobacco control. Relying on internal tobacco industry documents, surveys and experimental data and drawing from political advocacy literature, we describe tobacco industry and public health research on the American Legacy Foundation's "truth" campaign, an example of effective negative advertising in the service of public health. The tobacco industry determined that the most effective advertisements run by Legacy's "truth" campaign were negative advertisements. Although the tobacco industry's own research suggested that these negative ads identified and effectively reframed the cigarette as a harmful consumer product rather than focusing solely on tobacco companies, Philip Morris accused Legacy of 'vilifying' it. Public health researchers have demonstrated the effectiveness of the "truth" campaign in reducing smoking initiation. Research on political advocacy demonstrating the value of negative advertising has rarely been used in the development of public health media campaigns, but negative advertising can effectively communicate certain public health messages and serve to counter corporate disease promotion.

Drinking Motives and Alcohol Outcome Expectancies as Mediators of the Association between Negative Urgency and Alcohol Consumption

PubMed Central

Anthenien, Amber M.; Lembo, Jordanna; Neighbors, Clayton

2017-01-01

Objective To determine whether the effects of negative urgency, a unique facet of impulsivity marked by engaging in potentially unhealthy and rash behaviors in order to cope with anxiety or negative moods, on drinking behavior can be explained by positive and negative alcohol outcome expectancies and specific drinking motives (i.e., coping and enhancement). Methods College students (N = 194) completed web-based surveys in exchange for course credit. Students completed measures of negative urgency, comprehensive effects of alcohol, drinking motives, and alcohol use behaviors. Results Results of path analysis indicated significant indirect effects of negative urgency and alcohol use through both alcohol outcome expectancies and enhancement motives. The effects of enhancement motives on drinking were mediated by positive alcohol outcome expectancies. The effects of coping motives on drinking were not attributable to negative expectancies. Conclusions Individuals high on negative urgency may consume alcohol in order to ameliorate their emotional distress due to strong desires to increase positive and decrease negative experiences associated with drinking. Emotion-focused impulsivity’s influence on drinking outcomes can be ascribed to enhancement motives for drinking as well as positive and negative alcohol outcome expectancies. Prevention efforts should target drinking motives and alcohol outcome expectancies among those higher in negative urgency. PMID:27914226

Drinking motives and alcohol outcome expectancies as mediators of the association between negative urgency and alcohol consumption.

PubMed

Anthenien, Amber M; Lembo, Jordanna; Neighbors, Clayton

2017-03-01

To determine whether the effects of negative urgency, a unique facet of impulsivity marked by engaging in potentially unhealthy and rash behaviors in order to cope with anxiety or negative moods, on drinking behavior can be explained by positive and negative alcohol outcome expectancies and specific drinking motives (i.e., coping and enhancement). College students (N=194) completed web-based surveys in exchange for course credit. Students completed measures of negative urgency, comprehensive effects of alcohol, drinking motives, and alcohol use behaviors. Results of path analysis indicated significant indirect effects of negative urgency and alcohol use through both alcohol outcome expectancies and enhancement motives. The effects of enhancement motives on drinking were mediated by positive alcohol outcome expectancies. The effects of coping motives on drinking were not attributable to negative expectancies. Individuals high on negative urgency may consume alcohol in order to ameliorate their emotional distress due to strong desires to increase positive and decrease negative experiences associated with drinking. Emotion-focused impulsivity's influence on drinking outcomes can be ascribed to enhancement motives for drinking as well as positive and negative alcohol outcome expectancies. Prevention efforts should target drinking motives and alcohol outcome expectancies among those higher in negative urgency. Copyright © 2016 Elsevier Ltd. All rights reserved.

Negative Life Events and Antenatal Depression among Pregnant Women in Rural China: The Role of Negative Automatic Thoughts.

PubMed

Wang, Yang; Wang, Xiaohua; Liu, Fangnan; Jiang, Xiaoning; Xiao, Yun; Dong, Xuehan; Kong, Xianglei; Yang, Xuemei; Tian, Donghua; Qu, Zhiyong

2016-01-01

Few studies have looked at the relationship between psychological and the mental health status of pregnant women in rural China. The current study aims to explore the potential mediating effect of negative automatic thoughts between negative life events and antenatal depression. Data were collected in June 2012 and October 2012. 495 rural pregnant women were interviewed. Depressive symptoms were measured by the Edinburgh postnatal depression scale, stresses of pregnancy were measured by the pregnancy pressure scale, negative automatic thoughts were measured by the automatic thoughts questionnaire, and negative life events were measured by the life events scale for pregnant women. We used logistic regression and path analysis to test the mediating effect. The prevalence of antenatal depression was 13.7%. In the logistic regression, the only socio-demographic and health behavior factor significantly related to antenatal depression was sleep quality. Negative life events were not associated with depression in the fully adjusted model. Path analysis showed that the eventual direct and general effects of negative automatic thoughts were 0.39 and 0.51, which were larger than the effects of negative life events. This study suggested that there was a potentially significant mediating effect of negative automatic thoughts. Pregnant women who had lower scores of negative automatic thoughts were more likely to suffer less from negative life events which might lead to antenatal depression.

[Progress of researches on the mechanism of cupping therapy].

PubMed

Cui, Shuai; Cui, Jin

2012-12-01

Cupping therapy of Chinese medicine is able to relieve a variety of diseases or clinical conditions, which results from the comprehensive effects of multiple types of stimulation exerted onto the regional acupoint areas. Among the stimuli, the negative pressure from cupping is one of the main factors inducing therapeutic effects. In the present paper, the authors review development of researches on the underlying mechanism of therapeutic effects of cupping-negative pressure from 1) the factor of intra-cup negative pressure; 2) influence of intra-cup negative pressure on cup-blackspot formation; 3) influence of cupping on regional blood vessels and blood flow; 4) effect of cupping on regional ultrastructure of the capillary in the raw-surface tissue; 5) effect of cupping-negative pressure on regional endothelial cells; and 6) biological effects of negative pressure drainage. Generally, cupping induced negative pressure can dilate local blood vessels to improve microcirculation, promote capillary endothelial cells repair, accelerate granulation and angiogenesis, etc., in the regional tissues, normalizing the patients' functional state at last.

Negative control exposure studies in the presence of measurement error: implications for attempted effect estimate calibration

PubMed Central

Sanderson, Eleanor; Macdonald-Wallis, Corrie; Davey Smith, George

2018-01-01

Abstract Background Negative control exposure studies are increasingly being used in epidemiological studies to strengthen causal inference regarding an exposure-outcome association when unobserved confounding is thought to be present. Negative control exposure studies contrast the magnitude of association of the negative control, which has no causal effect on the outcome but is associated with the unmeasured confounders in the same way as the exposure, with the magnitude of the association of the exposure with the outcome. A markedly larger effect of the exposure on the outcome than the negative control on the outcome strengthens inference that the exposure has a causal effect on the outcome. Methods We investigate the effect of measurement error in the exposure and negative control variables on the results obtained from a negative control exposure study. We do this in models with continuous and binary exposure and negative control variables using analysis of the bias of the estimated coefficients and Monte Carlo simulations. Results Our results show that measurement error in either the exposure or negative control variables can bias the estimated results from the negative control exposure study. Conclusions Measurement error is common in the variables used in epidemiological studies; these results show that negative control exposure studies cannot be used to precisely determine the size of the effect of the exposure variable, or adequately adjust for unobserved confounding; however, they can be used as part of a body of evidence to aid inference as to whether a causal effect of the exposure on the outcome is present. PMID:29088358

Negative control exposure studies in the presence of measurement error: implications for attempted effect estimate calibration.

PubMed

Sanderson, Eleanor; Macdonald-Wallis, Corrie; Davey Smith, George

2018-04-01

Negative control exposure studies are increasingly being used in epidemiological studies to strengthen causal inference regarding an exposure-outcome association when unobserved confounding is thought to be present. Negative control exposure studies contrast the magnitude of association of the negative control, which has no causal effect on the outcome but is associated with the unmeasured confounders in the same way as the exposure, with the magnitude of the association of the exposure with the outcome. A markedly larger effect of the exposure on the outcome than the negative control on the outcome strengthens inference that the exposure has a causal effect on the outcome. We investigate the effect of measurement error in the exposure and negative control variables on the results obtained from a negative control exposure study. We do this in models with continuous and binary exposure and negative control variables using analysis of the bias of the estimated coefficients and Monte Carlo simulations. Our results show that measurement error in either the exposure or negative control variables can bias the estimated results from the negative control exposure study. Measurement error is common in the variables used in epidemiological studies; these results show that negative control exposure studies cannot be used to precisely determine the size of the effect of the exposure variable, or adequately adjust for unobserved confounding; however, they can be used as part of a body of evidence to aid inference as to whether a causal effect of the exposure on the outcome is present.

Stressful Life Event Influences on Positive and Negative Psychological Functioning.

ERIC Educational Resources Information Center

McGowan, John R.; Cohen, Lawrence H.

Some research has suggested that positive life events may interact with negative life events during periods of high stress to buffer the effects of negative events. The relationships among positive and negative life events and positive and negative psychological status were examined in an investigation of the direct and mediating effects of…

The Peculiar Negative Greenhouse Effect Over Antarctica

NASA Astrophysics Data System (ADS)

Sejas, S.; Taylor, P. C.; Cai, M.

2017-12-01

Greenhouse gases warm the climate system by reducing the energy loss to space through the greenhouse effect. Thus, a common way to measure the strength of the greenhouse effect is by taking the difference between the surface longwave (LW) emission and the outgoing LW radiation. Based on this definition, a paradoxical negative greenhouse effect is found over the Antarctic Plateau, which suprisingly indicates that greenhouse gases enhance energy loss to space. Using 13 years of NASA satellite observations, we verify the existence of the negative greenhouse effect and find that the magnitude and sign of the greenhouse effect varies seasonally and spectrally. A previous explanation attributes the negative greenhouse effect solely to stratospheric CO2 and warmer than surface stratospheric temperatures. However, we surprisingly find that the negative greenhouse effect is predominantly caused by tropospheric water vapor. A novel principle-based explanation provides the first complete account of the Antarctic Plateau's negative greenhouse effect indicating that it is controlled by the vertical variation of temperature and greenhouse gas absorption strength. Our findings indicate that the strong surface-based temperature inversion and scarcity of free tropospheric water vapor over the Antarctic Plateau cause the negative greenhouse effect. These are climatological features uniquely found in the Antarctic Plateau region, explaining why the greenhouse effect is positive everywhere else.

Turning negative into positive: public health mass media campaigns and negative advertising

PubMed Central

Apollonio, D. E.; Malone, R. E.

2009-01-01

Literature suggests that ‘negative advertising’ is an effective way to encourage behavioral changes, but it has enjoyed limited use in public health media campaigns. However, as public health increasingly focuses on non-communicable disease prevention, negative advertising could be more widely applied. This analysis considers an illustrative case from tobacco control. Relying on internal tobacco industry documents, surveys and experimental data and drawing from political advocacy literature, we describe tobacco industry and public health research on the American Legacy Foundation’s “truth” campaign, an example of effective negative advertising in the service of public health. The tobacco industry determined that the most effective advertisements run by Legacy’s “truth” campaign were negative advertisements. Although the tobacco industry’s own research suggested that these negative ads identified and effectively reframed the cigarette as a harmful consumer product rather than focusing solely on tobacco companies, Philip Morris accused Legacy of ‘vilifying’ it. Public health researchers have demonstrated the effectiveness of the “truth” campaign in reducing smoking initiation. Research on political advocacy demonstrating the value of negative advertising has rarely been used in the development of public health media campaigns, but negative advertising can effectively communicate certain public health messages and serve to counter corporate disease promotion. PMID:18948569

Does infant negative emotionality moderate the effect of maternal depression on motor development?

PubMed

Sacchi, C; De Carli, P; Vieno, A; Piallini, G; Zoia, S; Simonelli, A

2018-04-01

Maternal depression represents an important social/environmental factor in early childhood; however, its effect on children's motor development may vary depending on the role of infants' dispositional variables. The objective of this study is to investigate the effect of the interaction between maternal depressive symptoms in the first two years of a child's life and the child's temperamental negative emotionality on motor development during this time. Using a cross-sectional study, we assessed 272 infants aged 0 to 24 months old and their mothers. We measured the following variables: maternal depression, infant's negative emotionality, and motor development. A three-way interaction effect highlights that negative emotionality in infants and maternal depression together affect children's overall motor growth trajectory. Infants with low negative emotionality display no effect of maternal depression on motor development. Conversely, infants with high negative emotionality seem to be more susceptible to the effect of maternal depression. Specifically, high maternal depression tends to foster the negative effect of infant's negativity on motor development across time, albeit not significantly. Finally, the absence of maternal depression significantly buffers negative temperament in infants. Findings highlighted the importance of integrating different perspectives when describing early motor growth. In fact, only when considering the interdependence of potential predictors their effect on the motor growth significantly emerges. Screening for early temperamental vulnerability might help in tailoring interventions to prevent maternal depression from affecting infants' motor development. Copyright © 2018 Elsevier B.V. All rights reserved.

How encompassing is the effect of negativity bias on political conservatism?

PubMed

Malka, Ariel; Soto, Christopher J

2014-06-01

We argue that the political effects of negativity bias are narrower than Hibbing et al. suggest. Negativity bias reliably predicts social, but not economic, conservatism, and its political effects often vary across levels of political engagement. Thus the role of negativity bias in broad ideological conflict depends on the strategic packaging of economic and social attitudes by political elites.

Negative dendritic effect on enzymatic hydrolysis of dendrimer conjugates.

PubMed

Zhou, Zhengwei; Cong, Mei; Li, Mengyao; Tintaru, Aura; Li, Jia; Yao, Jianhua; Xia, Yi; Peng, Ling

2018-06-08

Dendrimers possess intriguing "dendritic effects", which are unique characteristics that stem from the dendrimer generation and size. Here we report a "negative dendritic effect" observed during enzymatic hydrolysis of dendrimer conjugates. Such negative dendritic effects, though rarely reported, may be explored for tailored and generation-dependent drug release.

Negative Treatment Effects: Is It Time for a Black Box Warning?

ERIC Educational Resources Information Center

Boisvert, Charles M.

2010-01-01

Comments on Negative effects from psychological treatments: A perspective by David Barlow. The author addresses negative treatment effects in the psychotherapy field by stating that Barlow provided a historical perspective of clinical psychology's long-standing interest in studying the positive effects of psychotherapy, and he indicated that…

Spectroscopic characterization of the oxyferrous complex of prostacyclin synthase in solution and in trapped sol–gel matrix

PubMed Central

Yeh, Hui-Chun; Hsu, Pei-Yung; Tsai, Ah-Lim; Wang, Lee-Ho

2010-01-01

Prostacyclin synthase (PGIS) is a member of the cytochrome P450 family in which the oxyferrous complexes are generally labile in the absence of substrate. At 4 °C, the on-rate constants and off-rate constants of oxygen binding to PGIS in solution are 5.9 × 105 m−1 ·s−1 and 29 s−1, respectively. The oxyferrous complex decays to a ferric form at a rate of 12 s−1. We report, for the first time, a stable oxyferrous complex of PGIS in a transparent sol–gel monolith. The encapsulated ferric PGIS retained the same spectroscopic features as in solution. The binding capabilities of the encapsulated PGIS were demonstrated by spectral changes upon the addition of O-based, N-based and C-based ligands. The peroxidase activity of PGIS in sol–gel was three orders of magnitude slower than that in solution owing to the restricted diffusion of the substrate in sol–gel. The oxyferrous complex in sol–gel was observable for 24 h at room temperature and displayed a much red-shifted Soret peak. Stabilization of the ferrous–carbon monoxide complex in sol–gel was observed as an enrichment of the 450-nm species over the 420-nm species. This result suggests that the sol–gel method may be applied to other P450s to generate a stable intermediate in the di-oxygen activation. PMID:18397321

Application of MCD spectroscopy and TD-DFT to a highly non-planar porphyrinoid ring system. New insights on red-shifted porphyrinoid spectral bands.

PubMed

Mack, John; Asano, Yoshiaki; Kobayashi, Nagao; Stillman, Martin J

2005-12-21

The first magnetic circular dichroism (MCD) spectra are reported for tetraphenyltetraacenaphthoporphyrin (TPTANP). The impact on the electronic structure of steric interactions between the fused acenaphthalene rings and the meso-tetraphenyl substituents is explored based on an analysis of the optical spectra of the Zn(II) complex (ZnTPTANP) and the free base dication species ([H4TPTANP]2+). In the case of ZnTPTANP, significant folding of the porphyrinoid ligand induces a highly unusual MCD-sign reversal providing the first direct spectroscopic evidence of ligand nonplanarity. Density functional theory (DFT) geometry optimizations for a wide range of Zn(II) porphyrinoids based on the B3LYP functional and TD-DFT calculations of the associated UV-visible absorption spectra are reported, allowing a complete assessment of the MCD data. TPTANP complexes are found to fall into a class of cyclic polyenes, termed as soft MCD chromophores by Michl (J. Pure Appl. Chem. 1980, 52, 1549.), since the signs of the Faraday A1 terms observed in the MCD spectrum are highly sensitive to slight structural changes. The origin of an unusually large red shift of the main B (or Soret) band of MTPTANP (the most red shifted ever reported for fused-ring-expanded metal porphines) and of similar red shifts observed in the spectra of other peripherally crowded porphyrinoid complexes is also explored and explained on this basis.

Palladium-directed self-assembly of multi-titanium(IV)-porphyrin arrays on the substrate surface as sensitive ultrathin films for hydrogen peroxide sensing, photocurrent generation, and photochromism of viologen

NASA Astrophysics Data System (ADS)

He, Wen-Li; Fang, Fang; Ma, Dong-Mei; Chen, Meng; Qian, Dong-Jin; Liu, Minghua

2018-01-01

Multiporphyrin arrays are large, π-conjugated chromophores with high absorption efficiency and strong chemical stability that play an important role in supramolecular and advanced material sciences. Palladium-directed self-assembly of multiporphyrin array ultrathin films was achieved on substrate surfaces using oxo[5,10,15,20-tetra(4-pyridyl)porphyrinato]titanium (IV) complex [TiO(TPyP)] as a linker and sodium tetrachloropalladate (Na2PdCl4) as a connector. The Pd-TiOTPyP films as prepared were characterized by using UV-vis absorption and X-ray photoelectron spectroscopy, as well as by atomic force and scanning electron microscopy. The Soret absorption band of TiOTPyP was observed to red shift by 6 nm when the Pd-TiOTPyP multilayer-modified quartz substrate was immersed in an aqueous solution containing hydrogen peroxide. This was attributed to the formation of a TiO2TPyP monoperoxo complex. This oxidation reaction could be accelerated in an acidic solution. Furthermore, the immobilized Pd-TiOTPyP multilayers could act as light-harvesting units for photocurrent generation and photochromism of viologens, with strong stability, reproducibility, and recyclability. The photocurrent density could be enhanced in electrolyte solutions containing electron donors such as triethanolamine, or electron acceptors such as viologens. Finally, photoinduced reduction (photochromism) of viologens was investigated using the Pd-TiOTPyP multilayers as light sensitizers and EDTA as the electron donors.

In vitro photodynamic activity of lipid vesicles with zinc phthalocyanine derivative against Enterococcus faecalis.

PubMed

Sobotta, Lukasz; Dlugaszewska, Jolanta; Kasprzycki, Piotr; Lijewski, Sebastian; Teubert, Anna; Mielcarek, Jadwiga; Gdaniec, Maria; Goslinski, Tomasz; Fita, Piotr; Tykarska, Ewa

2018-06-01

Zinc(II) phthalocyanine bearing eight non-peripheral 2-propoxy substituents was subjected to physicochemical study and, after incorporation in lipid vesicles, assessed as a potential photosensitizer for antibacterial photodynamic therapy. The phthalocyanine derivative obtained in the macrocyclization reaction was characterized by MS and NMR techniques. Moreover, its chemical purity was confirmed by HPLC analysis. X-ray structural analysis revealed that overcrowding of the phthalocyanine derivative leads to a strong out-of-plane distortion of the π-system of the macrocycle core. In the UV-Vis absorption spectra of zinc(II) phthalocyanine two characteristic bands were found: the Soret (300-450 nm) and the Q band (600-800 nm). Photophysical properties of mono- and diprotonated forms of phthalocyanine derivative were studied with time-resolved fluorescence spectroscopy. Its tri- and tetraprotonated forms could not be obtained, because compound decomposes in higher acid concentrations. The presented zinc(II) phthalocyanine showed values of singlet oxygen generation Φ Δ  = 0.18 and 0.16, the quantum yield of the photodecomposition Φ P  = 3.06∙10 -4 and 1.23∙10 -5 and the quantum yield of fluorescence Φ FL  = 0.005 and 0.004, designated in DMF and DMSO, respectively. For biological studies, phthalocyanine has been incorporated into modified liposome vesicles containing ethanol. In vitro bacteria photoinactivation study revealed no activity against Escherichia coli and 5.7 log reduction of the Enterococcus faecalis growth. Copyright © 2018 Elsevier B.V. All rights reserved.

Crystallochemistry and origin of pyroxenes in komatiites

NASA Astrophysics Data System (ADS)

Bouquain, Sebastien; Arndt, N. T.; Hellebrand, E.; Faure, F.

2009-11-01

We present a detailed mineralogical and major- and trace-element study of pyroxenes in two Archean komatiitic flows in Alexo, Canada. The pyroxenes in spinifex-textured lavas commonly are zoned with cores of magnesian pigeonite and rims of augite. Concentrations of incompatible trace elements are low in pigeonite and jump to higher values in the augite mantles, a variation that can be modelled using accepted partition coefficients and assuming crystallization from komatiitic liquids. Crystallization sequences are very different in different parts of both flows. In the flow top, the sequence is olivine followed by augite: deeper in the spinifex sequence, pigeonite crystallizes after olivine, followed by augite; in lower cumulates, orthopyroxene or augite accompany olivine. In spinifex lavas, pigeonite crystallizes sooner than would be predicted on the basis of equilibrium phase relations. We propose that contrasting crystallization sequences depend on the position in the flow and on the conditions of crystal growth. In the flowtop, rapid cooling causes quench crystallization. Deeper in the spinifex layer, constrained growth in a thermal gradient, perhaps augmented by Soret differentiation, accounts for the early crystallization of pigeonite. The cumulus minerals represent a near-equilibrium assemblage. Augites in Al-undepleted Archean komatiites in various localities in Canada and Zimbabwe have high moderate to high Wo contents but their Mg# (Mg/(Mg + Fe) are lower than in augites in komatiites from Barberton, South Africa. We attribute the combination of high Wo and high Mg# in Barberton rocks to the unusually high CaO/Al2O3 of these Al-depleted komatiites.

Electron-Deficient Near-Infrared Pt(II) and Pd(II) Benzoporphyrins with Dual Phosphorescence and Unusually Efficient Thermally Activated Delayed Fluorescence: First Demonstration of Simultaneous Oxygen and Temperature Sensing with a Single Emitter.

PubMed

Zach, Peter W; Freunberger, Stefan A; Klimant, Ingo; Borisov, Sergey M

2017-11-01

We report a family of Pt and Pd benzoporphyrin dyes with versatile photophysical properties and easy access from cheap and abundant chemicals. Attaching 4 or 8 alkylsulfone groups onto a meso-tetraphenyltetrabenzoporphyrin (TPTBP) macrocylcle renders the dyes highly soluble in organic solvents, photostable, and electron-deficient with the redox potential raised up to 0.65 V versus the parent porphyrin. The new dyes intensively absorb in the blue (Soret band, 440-480 nm) and in the red (Q-band, 620-650 nm) parts of the electromagnetic spectrum and show bright phosphorescence at room-temperature in the NIR with quantum yields up to 30% in solution. The small singlet-triplet energy gap yields unusually efficient thermally activated delayed fluorescence (TADF) at elevated temperatures in solution and in polymeric matrices with quantum yields as high as 27% at 120 °C, which is remarkable for benzoporphyrins. Apart from oxygen sensing, these properties enable unprecedented simultaneous, self-referenced oxygen and temperature sensing with a single indicator dye: whereas oxygen can be determined either via the decay time of phosphorescence or TADF, the temperature is accessed via the ratio of the two emissions. Moreover, the dyes are efficient sensitizers for triplet-triplet annihilation (TTA)-based upconversion making possible longer sensitization wavelength than the conventional benzoporphyrin complexes. The Pt-octa-sulfone dye also features interesting semireversible transformation in basic media, which generates new NIR absorbing species.

Follow up on the crystal growth experiments of the LDEF

NASA Technical Reports Server (NTRS)

Nielsen, K. F.; Lind, M. D.

1993-01-01

The results of the 4 solution growth experiments on the LDEF have been published elsewhere. Both the crystals of CaCO3, which were large and well shaped, and the much smaller TTF-TCNQ crystals showed unusual morphological behavior. The follow up on these experiments was begun in 1981, when ESA initiated a 'Concept Definition Study' on a large, 150 kg, Solution Growth Facility (SGF) to be included in the payload of EURECA-1, the European Retrievable Carrier. This carrier was a continuation of the European Spacelab and at that time planned for launch in 1987. The long delay of the LDEF retrieval and of subsequent missions brought about reflections both on the concept of crystal growth in space and on the choice of crystallization materials that had been made for the LDEF. Already before the LDEF retrieval, research on TTF-TCNQ had been stopped, and a planned growth experiment with TTF-TCNQ on the SGF/EURECA had been cancelled. The target of the SGF investigation is now more fundamental in nature. None of the crystals to be grown here are, like TTF-TCNQ, in particular demand by science or industry, and the crystals only serve the purpose of model crystals. The real purpose of the investigation is to study the growth behavior. One of the experiments, the Soret Coefficient Measurement experiment is not growing crystals at all, but has it as its sole purpose to obtain accurate information on thermal diffusion, a process of importance in crystal growth from solution.

A spectroscopic and thermodynamic study of porphyrin/DNA supramolecular assemblies.

PubMed Central

Pasternack, R F; Goldsmith, J I; Szép, S; Gibbs, E J

1998-01-01

Assemblies of trans-bis(N-methylpyridinium-4-yl)diphenylporphine ions on the surface of calf thymus DNA have been studied using several spectroscopic techniques: absorbance, circular dichroism, and resonance light scattering. The aggregation equilibrium can be treated as a two-state system-monomer and assembly-each bound to the nucleic acid template. The aggregate absorption spectrum in the Soret region is resolved into two bands of Lorentzian line shape, while the DNA-bound monomer spectrum in this region is composed of two Gaussian bands. The Beer-Lambert law is obeyed by both porphyrin forms. The assembly is also characterized by an extremely large, bisignate induced circular dichroism (CD) profile and by enhanced resonance light scattering (RLS). Both the CD and RLS intensities depend linearly on aggregate concentration. The RLS result is consistent with a model for the aggregates as being either of a characteristic size or of a fixed distribution of sizes, independent of total porphyrin concentration or ionic strength. Above threshold values of concentration and ionic strength, the mass action expression for the equilibrium has a particularly simple form: K' = cac-1; where cac is defined as the "critical assembly concentration."offe dependence of the cac upon temperature and ionic strength (NaCl) has been investigated at a fixed DNA concentration. The value of the cac scales as the inverse square of the sodium chloride concentration and, from temperature dependence studies, the aggregation process is shown to be exothermic. PMID:9675203

Presence of exclusively bacteriochlorophyll-c containing substrain in the culture of green sulfur photosynthetic bacterium Chlorobium vibrioforme strain NCIB 8327 producing bacteriochlorophyll-d.

PubMed

Saga, Yoshitaka; Oh-oka, Hirozo; Hayashi, Takashi; Tamiaki, Hitoshi

2003-12-01

The light-dependent composition change of light harvesting bacteriochlorophyll(BChl)s in the present culture of a green sulfur photosynthetic bacterium Chlorobium (Chl.) vibrioforme f. sp. thiosulfatophilum strain NCIB 8327 was investigated by visible absorption spectroscopy and HPLC analyses. When the culture was repeatedly grown in liquid media under a low light condition, both the Soret and Qy absorption bands of the in vivo spectrum were shifted to longer wavelengths. Analysis of the extracted pigments by HPLC revealed that the ratio of the amount of BChl-c to that of BChl-d molecules gradually increased during repeated cultivation. In contrast, when the culture grown under a low light intensity was transferred to a high light condition and continued to be grown, the absorption bands were shifted to shorter wavelengths and the ratio of BChls-c/d decreased finally to the almost original value. Colonies were prepared on solid agar media from the liquid culture containing both BChls-c and d, which was grown under a low light intensity. Each colony obtained was found to contain either BChl-c or d, but not both of them. Two types of cells isolated in this study were derived from the same clone, judged from their genetic analyses. The variation of pigment composition in our liquid culture observed here could be ascribed to the difference of growth rates between two substrains containing BChl-c and BChl-d, respectively, depending on light conditions.

Alterations of pigment composition and their interactions in response to different light conditions in the diatom Chaetoceros gracilis probed by time-resolved fluorescence spectroscopy.

PubMed

Nagao, Ryo; Ueno, Yoshifumi; Yokono, Makio; Shen, Jian-Ren; Akimoto, Seiji

2018-07-01

Maintenance of energy balance under changeable light conditions is an essential function of photosynthetic organisms to achieve efficient photochemical reactions. Among the photosynthetic organisms, diatoms possess light-harvesting fucoxanthin chlorophyll (Chl) a/c-binding protein (FCP) as peripheral antennas. However, how diatoms regulate excitation-energy distribution between FCP and the two photosystem cores during light adaptation is poorly understood. In this study, we examined spectroscopic properties of a marine diatom Chaetoceros gracilis adapted in the dark and at photosynthetic photon flux density at 30 and 300 μmol photons m -2  s -1 . Absorption spectra at 77 K showed significant changes in the Soret region, and 77-K steady-state fluorescence spectra showed significant differences in the spectral shape and relative fluorescence intensity originating from both PSII and PSI, among the cells grown under different light conditions. These results suggest alterations of pigment composition and their interactions under the different light conditions. These alterations affected the excitation-energy dynamics monitored by picosecond time-resolved fluorescence analyses at 77 K significantly. The contributions of Chls having lower energy levels than the reaction center Chls in the two photosystems to the energy dynamics were clearly identified in the three cells but with presumably different roles. These findings provide insights into the regulatory mechanism of excitation-energy balance in diatoms under various light conditions. Copyright © 2018 Elsevier B.V. All rights reserved.

Social inhibition modulates the effect of negative emotions on cardiac prognosis following percutaneous coronary intervention in the drug-eluting stent era.

PubMed

Denollet, Johan; Pedersen, Susanne S; Ong, Andrew T L; Erdman, Ruud A M; Serruys, Patrick W; van Domburg, Ron T

2006-01-01

Negative emotions have an adverse effect on cardiac prognosis. We investigated whether social inhibition (inhibited self-expression in social interaction) modulates the effect of negative emotions on clinical outcome following percutaneous coronary intervention (PCI). Eight hundred and seventy-five consecutive patients from the RESEARCH registry (Erasmus Medical Centre, Rotterdam) completed depression, anxiety, negativity (negative emotions in general), and social inhibition scales 6 months following PCI. The endpoint was major adverse cardiac event (MACE-death, myocardial infarction, coronary artery bypass graft (CABG), or PCI) at 9 months following assessment. There were 100 MACE; patients who were high in both negativity and inhibition were at increased risk of MACE (38/254=15%) when compared with high negativity/low inhibition patients (13/136=10%; P=0.018). Depression (P=0.23) or anxiety (P=0.63) did not explain away this moderating effect of inhibition. High negativity/high inhibition (HR=1.92, 95%CI 1.22-3.01, P=0.005) and previous CABG (HR=1.90, 95%CI 1.04-3.47, P=0.038) were independent predictors of MACE. Patients with high negativity but low inhibition were not at increased risk (P=0.76). High negativity/high inhibition also independently predicted death/MI (n=20) as a more specific endpoint (HR=5.85, P=0.001). The interaction effect of social inhibition and negative emotions, rather than negative emotions per se, predicted poor clinical outcome following PCI. Social inhibition should not be overlooked as a modulating factor.

Evaluating the Separate and Combined Effects of Positive and Negative Reinforcement on Task Compliance

ERIC Educational Resources Information Center

Bouxsein, Kelly J.; Roane, Henry S.; Harper, Tara

2011-01-01

Positive and negative reinforcement are effective for treating escape-maintained destructive behavior. The current study evaluated the separate and combined effects of these contingencies to increase task compliance. Results showed that a combination of positive and negative reinforcement was most effective for increasing compliance. (Contains 1…

Negative incidental emotions augment fairness sensitivity.

PubMed

Liu, Cuizhen; Chai, Jing Wen; Yu, Rongjun

2016-04-22

Previous studies have shown that task-unrelated emotions induced incidentally exert carryover effects on individuals' subsequent decisions in financial negotiations. However, the specificity of these emotion effects are not clear. In three experiments, we systematically investigated the role of seven transiently induced basic emotions (disgust, sadness, anger, fear, happiness, surprise and neutral) on rejection of unfair offers using the ultimatum game. We found that all negative emotions (disgust, sadness, anger and fear), but not happiness or surprise, significantly increased rejection rates, suggesting that the effect of incidental negative emotions on fairness is not specific to the type of negative emotion. Our findings highlight the role of fleeting emotions in biasing decision-making processes and suggest that all incidental negative emotions exert similar effects on fairness sensitivity, possibly by potentiating attention towards negative aspects of the situation.

Is There a Paradox of Aging: When the Negative Aging Stereotype Meets the Positivity Effect in Older Adults.

PubMed

Zhou, Liqing; Lu, Jia; Chen, Guopeng; Dong, Li; Yao, Yujia

2017-01-01

Background/Study Context: Socioemotional selectivity theory (SST) states that the positivity effect is a result of older adults' emotion regulation and that older adults derive more emotional satisfaction from prioritizing positive information processing. The authors explored whether the positivity effect appeared when the negative aging stereotype was activated in older adults and also whether the effect differed between mixed and unmixed valence conditions. Sixty younger (18-23 years of age) and 60 older (60-87 years of age) adults were randomly assigned to a control group and a priming group, in which the negative aging stereotype was activated. All the participants were asked to select 15 words that best described the elderly from a mixed-word list (positive and negative words were mixed together) and from an unmixed-word list (positive and negative words were separated). Older adults in the control group selected more positive words, whereas among younger adults, selection did not differ by valence in either the mixed- or unmixed-word list conditions. There were no differences between the positive and negative word choices of the younger and older adults in the priming group. We calculated the differences between the numbers of positive and negative words, and the differences in the older adults' word choices were larger than those among the younger adults; the differences were also larger in the control group than in the priming group. The positivity effect worked by choosing positive stimuli rather than avoiding negative stimuli. The role of emotion regulation in older adults was limited, and when the positivity effect faced the effect of the negative aging stereotype, the negative stereotype effect was dominant. Future research should explore the changes in the positivity effect in the face of a positive aging stereotype and what roles other factors (e.g., activation level of the stereotype, arousal level of affective words) might play.

Combinatorial Effects of Lapatinib and Rapamycin in Triple-Negative Breast Cancer Cells

PubMed Central

Liu, Tongrui; Yacoub, Rami; Taliaferro-Smith, LaTonia D.; Sun, Shi-Yong; Graham, Tisheeka R.; Dolan, Ryan; Lobo, Christine; Tighiouart, Mourad; Yang, Lily; Adams, Amy; O'Regan, Ruth M.

2016-01-01

Triple-negative breast cancers, which lack estrogen receptor, progesterone receptor, and HER2/neu overexpression, account for approximately 15% of breast cancers, but occur more commonly in African Americans. The poor survival outcomes seen with triple-negative breast cancers patients are, in part, due to a lack of therapeutic targets. Epidermal growth factor receptor (EGFR) is overexpressed in 50% of triple-negative breast cancers, but EGFR inhibitors have not been effective in patients with metastatic breast cancers. However, mTOR inhibition has been shown to reverse resistance to EGFR inhibitors. We examined the combination effects of mTOR inhibition with EGFR inhibition in triple-negative breast cancer in vitro and in vivo. The combination of EGFR inhibition by using lapatinib and mTOR inhibition with rapamycin resulted in significantly greater cytotoxicity than the single agents alone and these effects were synergistic in vitro. The combination of rapamycin and lapatinib significantly decreased growth of triple-negative breast cancers in vivo compared with either agent alone. EGFR inhibition abrogated the expression of rapamycin-induced activated Akt in triple-negative breast cancer cells in vitro. The combination of EGFR and mTOR inhibition resulted in increased apoptosis in some, but not all, triple-negative cell lines, and these apoptotic effects correlated with a decrease in activated eukaryotic translation initiation factor (eIF4E). These results suggest that mTOR inhibitors could sensitize a subset of triple-negative breast cancers to EGFR inhibitors. Given the paucity of effective targeted agents in triple-negative breast cancers, these results warrant further evaluation. PMID:21690228

Interactive and Indirect Effects of Anxiety and Negative Urgency on Alcohol-Related Problems

PubMed Central

Menary, Kyle R.; Corbin, William R.; Leeman, Robert F.; Fucito, Lisa M.; Toll, Benjamin A.; DeMartini, Kelly; O’Malley, Stephanie S.

2015-01-01

Background Although drinking for tension reduction has long been posited as a risk factor for alcohol-related problems, studies investigating anxiety in relation to risk for alcohol problems have returned inconsistent results, leading researchers to search for potential moderators. Negative urgency (the tendency to become behaviorally dysregulated when experiencing negative affect) is a potential moderator of theoretical interest because it may increase risk for alcohol problems among those high in negative affect. The present study tested a cross-sectional mediated moderation hypothesis whereby an interactive effect of anxiety and negative urgency on alcohol problems is mediated through coping-related drinking motives. Method The study utilized baseline data from a hazardously drinking sample of young adults (N = 193) evaluated for participation in a randomized controlled trial of naltrexone and motivational interviewing for drinking reduction. Results The direct effect of anxiety on physiological dependence symptoms was moderated by negative urgency such that the positive association between anxiety and physiological dependence symptoms became stronger as negative urgency increased. Indirect effects of anxiety and negative urgency on alcohol problems (operating through coping motives) were also observed. Conclusions Although results of the current cross-sectional study require replication using longitudinal data, the findings suggest that the simultaneous presence of anxiety and negative urgency may be an important indicator of risk for AUDs via both direct interactive effects and indirect additive effects operating through coping motives. These findings have potentially important implications for prevention/intervention efforts for individuals who become disinhibited in the context of negative emotional states. PMID:26031346

The Emergence of Parent-Child Coercive Processes in Toddlerhood

PubMed Central

Chang, Hyein; Shaw, Daniel S.

2015-01-01

Parent-child coercion typically emerges in toddlerhood with the child’s first acts of willful defiance and the parent’s first disciplinary attempts. We explored how parents and children may contribute to this process by examining bidirectional and interactive effects between child and maternal negative behavior in 310 low-income, ethnically diverse boys. Using multiple informants and methods, child negative emotionality and maternal negative control were assessed at 18 months and child disruptive behavior and maternal negative control were measured at 24 months. Indicative of parent effects, maternal negative control at 18 months amplified the relation between children’s negative emotionality at 18 months and disruptive behavior at 24 months. Child effects were found in an unexpected direction such that children’s negative emotionality at 18 months predicted decreases in mothers’ negative control at 24 months. Findings are discussed within a transactional framework that emphasizes mutual influence of children and parents over the course of development. PMID:26068801

40 CFR 57.816 - Effect of negative recommendation.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 5 2010-07-01 2010-07-01 false Effect of negative recommendation. 57.816 Section 57.816 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS... Reduction Technology § 57.816 Effect of negative recommendation. No waiver of the interim requirement for...

Effects of Creative Thinking and Its Personality Determinants on Negative Emotion Regulation.

PubMed

Chiu, Fa-Chung; Hsu, Chih-Chun; Lin, Yao-Nan; Liu, Cheng-Hong; Chen, Hsueh-Chih; Lin, Chi-Hsiang

2018-01-01

This study investigated the relationship between creativity and negative emotion, and the effects of integrating creative insight into the reappraisal process on negative emotions. In Study 1, participants' creativity and baseline anxiety levels were measured; then anxiety was induced, and anxiety levels were reassessed. In Study 2, participants wrote about past negative events and then completed the positive and negative affect schedule. They were split into three groups (insight reappraisal, simple reappraisal, or control groups); each of them received a separate intervention, and then they completed positive and negative affect schedule again. In Study 3, participants were randomly assigned to insight reappraisal or control groups; apart from measuring cognitive changes, the procedures were identical to Study 2. All participants were undergraduate students. Results showed that flexibility, originality, risk-taking, and complexity are negatively correlated with anxiety, and that insight reappraisal can induce insight experience and enhance cognitive changes, and reduce negative emotional responses. Therefore, integrating creative insight into the reappraisal process can enhance its effectiveness in reducing negative emotions.

Moderating effects of coping on work stress and job performance for nurses in tertiary hospitals: a cross-sectional survey in China.

PubMed

Li, Li; Ai, Hua; Gao, Lei; Zhou, Hao; Liu, Xinyan; Zhang, Zhong; Sun, Tao; Fan, Lihua

2017-06-12

Work stress is a major problem for nurses and it can negatively influence job performance. Therefore, it is critical to explore variables that can reduce or buffer the negative effects of work stress. This study explores the moderating effects of coping strategies on the relationship between work stress and job performance for nurses in China. A cross-sectional survey of 852 nurses from four tertiary hospitals in Heilongjiang Province, China, was conducted in 2013. Descriptive statistics were reported for socioeconomic status and demographic characteristics, level of work stress, coping strategies, and job performance. Regression analysis was conducted to test the interaction between work stress and coping strategies on job performance. Three subscales of work stress were negatively related to job performance. Positive coping strategies moderated Patient Care and job performance while negative coping strategies moderated Workload and Time and performance, and between Working Environment and Resources and performance. Positive coping strategies reduce or buffer the negative effects of work stress on job performance and negative coping strategies increased the negative effects.

The Unique Effects of Parental Alcohol and Affective Disorders, Parenting, and Parental Negative Affect on Adolescent Maladjustment

PubMed Central

Haller, Moira; Chassin, Laurie

2010-01-01

Using a high-risk community sample, multiple regression analyses were conducted separately for mothers (N=416) and fathers (N= 346) to test the unique, prospective influence of parental negative affect on adolescent maladjustment (internalizing symptoms, externalizing symptoms, and negative emotionality) two years later over and above parental alcohol and affective disorders, major disruption in the family environment, and parenting. Adolescent sex was tested as a moderator. Results indicated that maternal (but not paternal) negative affect had a unique, prospective effect on adolescent internalizing symptoms in girls and negative emotionality in both sexes, but did not predict adolescent externalizing symptoms. Findings demonstrate that mothers’ negative affect may have unique effects on adolescent adjustment, separate from the effects of clinically significant parental psychopathology, parenting, and disruption in the family environment. PMID:23761947

The Unique Effects of Parental Alcohol and Affective Disorders, Parenting, and Parental Negative Affect on Adolescent Maladjustment.

PubMed

Haller, Moira; Chassin, Laurie

2011-07-01

Using a high-risk community sample, multiple regression analyses were conducted separately for mothers ( N =416) and fathers ( N = 346) to test the unique, prospective influence of parental negative affect on adolescent maladjustment (internalizing symptoms, externalizing symptoms, and negative emotionality) two years later over and above parental alcohol and affective disorders, major disruption in the family environment, and parenting. Adolescent sex was tested as a moderator. Results indicated that maternal (but not paternal) negative affect had a unique, prospective effect on adolescent internalizing symptoms in girls and negative emotionality in both sexes, but did not predict adolescent externalizing symptoms. Findings demonstrate that mothers' negative affect may have unique effects on adolescent adjustment, separate from the effects of clinically significant parental psychopathology, parenting, and disruption in the family environment.

Negative incidental emotions augment fairness sensitivity

PubMed Central

Liu, Cuizhen; Chai, Jing Wen; Yu, Rongjun

2016-01-01

Previous studies have shown that task-unrelated emotions induced incidentally exert carryover effects on individuals’ subsequent decisions in financial negotiations. However, the specificity of these emotion effects are not clear. In three experiments, we systematically investigated the role of seven transiently induced basic emotions (disgust, sadness, anger, fear, happiness, surprise and neutral) on rejection of unfair offers using the ultimatum game. We found that all negative emotions (disgust, sadness, anger and fear), but not happiness or surprise, significantly increased rejection rates, suggesting that the effect of incidental negative emotions on fairness is not specific to the type of negative emotion. Our findings highlight the role of fleeting emotions in biasing decision-making processes and suggest that all incidental negative emotions exert similar effects on fairness sensitivity, possibly by potentiating attention towards negative aspects of the situation. PMID:27101931

Effectiveness and cost-effectiveness of body psychotherapy in the treatment of negative symptoms of schizophrenia--a multi-centre randomised controlled trial.

PubMed

Priebe, Stefan; Savill, Mark; Reininghaus, Ulrich; Wykes, Til; Bentall, Richard; Lauber, Christoph; McCrone, Paul; Röhricht, Frank; Eldridge, Sandra

2013-01-14

Negative symptoms of schizophrenia are frequently associated with poor long term outcomes. Established interventions have little, if any, positive effects on negative symptoms. Arts Therapies such as Body Psychotherapy (BPT) have been suggested to reduce negative symptoms, but the existing evidence is limited. In a small exploratory trial a manualised form of group BPT led to significantly lower negative symptom levels both at the end of treatment and at 4 months follow-up as compared to supportive counseling. We designed a large multi-site trial to assess the effectiveness of a manualised BPT intervention in reducing negative symptoms, compared to an active control. In a randomised controlled trial, 256 schizophrenic outpatients with negative symptoms will be randomly allocated either to BPT or Pilates groups. In both conditions, patients will be offered two 90 minutes sessions per week in groups of about 8 patients over a period of 10 weeks. Outcomes are assessed at the end of treatment and at six months follow-up. The primary outcome is severity of negative symptoms, as measured by the Positive and Negative Symptom Scale (PANSS), whilst a range of secondary outcome measures include general psychopathology, social contacts, and quality of life. We will also assess the cost-effectiveness of the intervention. The study aims to evaluate the effectiveness of a promising form of group therapy which may help alleviate negative symptoms that are associated with unfavourable long-term outcomes and have so far been difficult to treat. If the trial is successful, it will add a new and effective option in the treatment of negative symptoms. Group BPT is manualised, might be attractive to many patients because of its unusual approach, and could potentially be rolled out to services at relatively little additional cost. Current Controlled Trials ISRCTN84216587.

Effectiveness and cost-effectiveness of body psychotherapy in the treatment of negative symptoms of schizophrenia – a multi-centre randomised controlled trial

PubMed Central

2013-01-01

Background Negative symptoms of schizophrenia are frequently associated with poor long term outcomes. Established interventions have little, if any, positive effects on negative symptoms. Arts Therapies such as Body Psychotherapy (BPT) have been suggested to reduce negative symptoms, but the existing evidence is limited. In a small exploratory trial a manualised form of group BPT led to significantly lower negative symptom levels both at the end of treatment and at 4 months follow-up as compared to supportive counseling. We designed a large multi-site trial to assess the effectiveness of a manualised BPT intervention in reducing negative symptoms, compared to an active control. Methods/Design In a randomised controlled trial, 256 schizophrenic outpatients with negative symptoms will be randomly allocated either to BPT or Pilates groups. In both conditions, patients will be offered two 90 minutes sessions per week in groups of about 8 patients over a period of 10 weeks. Outcomes are assessed at the end of treatment and at six months follow-up. The primary outcome is severity of negative symptoms, as measured by the Positive and Negative Symptom Scale (PANSS), whilst a range of secondary outcome measures include general psychopathology, social contacts, and quality of life. We will also assess the cost-effectiveness of the intervention. Discussion The study aims to evaluate the effectiveness of a promising form of group therapy which may help alleviate negative symptoms that are associated with unfavourable long-term outcomes and have so far been difficult to treat. If the trial is successful, it will add a new and effective option in the treatment of negative symptoms. Group BPT is manualised, might be attractive to many patients because of its unusual approach, and could potentially be rolled out to services at relatively little additional cost. Trial registration Current Controlled Trials ISRCTN84216587 PMID:23317474

40 CFR 57.816 - Effect of negative recommendation.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 5 2011-07-01 2011-07-01 false Effect of negative recommendation. 57... Reduction Technology § 57.816 Effect of negative recommendation. No waiver of the interim requirement for... or a State first takes into account the Administrator's report, findings, and recommendations as to...

There was not, they did not: May negation cause the negated ideas to be remembered as existing?

PubMed Central

2017-01-01

In this article we demonstrate that negation of ideas can have paradoxical effects, possibly leading the listener to believe that the negated ideas actually existed. In Experiment 1, participants listened to a description of a house, in which some objects were mentioned, some were negated, and some were not mentioned at all. When questioned about the existence of these objects a week later, the participants gave more false positives for items that were negated in the original material than for items that were not mentioned at all, an effect we call negation related false memories (NRFM). The NRFM effect was replicated again in Experiment 2 with a sample of five and six year-old children. Experiment 3 confirmed NRFM in the case of negated actions. The results are discussed in terms of retention hypothesis, as well as the theory that negation can activate a representation of an entity and behaviour. It is also indicated that future research is needed to ensure that it is indeed negation which caused false alarms, not merely mentioning an object. PMID:28448549

Negative affectivity: moderator or confound in emotional dissonance-outcome relationships?

PubMed

Abraham, R

1999-01-01

This study was an examination of the impact of negative affectivity on relationships between emotional dissonance, job satisfaction, and emotional exhaustion. Negative affectivity is the predisposition to view life in negative terms. Emotional dissonance originates from the conflict between expressed and experienced emotions. In organizations that require the expression of positive emotions, high negative affectivity individuals may experience conflict between expressed, positive emotions and felt, negative emotions. A moderator effect exists when high negative affectivity individuals experience greater job dissatisfaction and emotional exhaustion. Alternatively, negative affectivity may exert a confounding effect through its relationship to both emotional dissonance and its outcomes. Empirical tests showed that negative affectivity moderated the emotional dissonance-job satisfaction relationship and confounded the emotional dissonance-emotional exhaustion relationship.

Brain Processing of Emotional Scenes in Aging: Effect of Arousal and Affective Context

PubMed Central

Mathieu, Nicolas Gilles; Gentaz, Edouard; Harquel, Sylvain; Vercueil, Laurent; Chauvin, Alan; Bonnet, Stéphane; Campagne, Aurélie

2014-01-01

Research on emotion showed an increase, with age, in prevalence of positive information relative to negative ones. This effect is called positivity effect. From the cerebral analysis of the Late Positive Potential (LPP), sensitive to attention, our study investigated to which extent the arousal level of negative scenes is differently processed between young and older adults and, to which extent the arousal level of negative scenes, depending on its value, may contextually modulate the cerebral processing of positive (and neutral) scenes and favor the observation of a positivity effect with age. With this aim, two negative scene groups characterized by two distinct arousal levels (high and low) were displayed into two separate experimental blocks in which were included positive and neutral pictures. The two blocks only differed by their negative pictures across participants, as to create two negative global contexts for the processing of the positive and neutral pictures. The results show that the relative processing of different arousal levels of negative stimuli, reflected by LPP, appears similar between the two age groups. However, a lower activity for negative stimuli is observed with the older group for both tested arousal levels. The processing of positive information seems to be preserved with age and is also not contextually impacted by negative stimuli in both younger and older adults. For neutral stimuli, a significantly reduced activity is observed for older adults in the contextual block of low-arousal negative stimuli. Globally, our study reveals that the positivity effect is mainly due to a modulation, with age, in processing of negative stimuli, regardless of their arousal level. It also suggests that processing of neutral stimuli may be modulated with age, depending on negative context in which they are presented to. These age-related effects could contribute to justify the differences in emotional preference with age. PMID:24932857

The Effects of Anger, Sadness and Happiness on Persuasive Message Processing: A Test of the Negative State Relief Model.

ERIC Educational Resources Information Center

Mitchell, Monique M.; Brown, Kenneth M.; Morris-Villagran, Melinda; Villagran, Paul D.

2001-01-01

Examines the strength of the effects of happiness and sadness on attitude change, and compares these effects with the effect of anger on attitude change and persuasive message processing. Finds that message strength was positively correlated with attitude, intention and behavior, but was negatively correlated with negative thoughts, and counter…

Exploring the Relationship between Negative Urgency and Dysregulated Eating: Etiologic Associations and the Role of Negative Affect

PubMed Central

Racine, Sarah E.; Keel, Pamela K.; Burt, S. Alexandra; Sisk, Cheryl L.; Neale, Michael; Boker, Steven; Klump, Kelly L.

2013-01-01

Negative urgency (i.e., the tendency to engage in rash action in response to negative affect) has emerged as a critical personality trait contributing to individual differences in binge eating. However, studies investigating the extent to which genetic and/or environmental influences underlie the effects of negative urgency on binge eating are lacking. Moreover, it remains unclear whether negative urgency-binge eating associations are simply due to the well-established role of negative affect in the development/maintenance of binge eating. The current study addresses these gaps by examining phenotypic and etiologic associations between negative urgency, negative affect, and dysregulated eating (i.e., binge eating, emotional eating) in a sample of 222 same-sex female twin pairs from the Michigan State Twin Registry. Negative urgency was significantly associated with both dysregulated eating symptoms, even after controlling for the effects of negative affect. Genetic factors accounted for the majority (62–77%) of this phenotypic association, although a significant proportion of this genetic covariation was due to genetic influences in common with negative affect. Non-shared environmental factors accounted for a relatively smaller (23–38%) proportion of the association, but these non-shared environmental effects were independent of negative affect. Findings suggest that the presence of emotion-based rash action, combined with high levels of negative affect, may significantly increase genetic risk for dysregulated eating. PMID:23356217

Exploring the relationship between negative urgency and dysregulated eating: etiologic associations and the role of negative affect.

PubMed

Racine, Sarah E; Keel, Pamela K; Burt, S Alexandra; Sisk, Cheryl L; Neale, Michael; Boker, Steven; Klump, Kelly L

2013-05-01

Negative urgency (i.e., the tendency to engage in rash action in response to negative affect) has emerged as a critical personality trait contributing to individual differences in binge eating. However, studies investigating the extent to which genetic and/or environmental influences underlie the effects of negative urgency on binge eating are lacking. Moreover, it remains unclear whether negative urgency-binge eating associations are simply a result of the well-established role of negative affect in the development/maintenance of binge eating. The current study addresses these gaps by examining phenotypic and etiologic associations between negative urgency, negative affect, and dysregulated eating (i.e., binge eating, emotional eating) in a sample of 222 same-sex female twin pairs from the Michigan State University Twin Registry. Negative urgency was significantly associated with both dysregulated eating symptoms, even after controlling for the effects of negative affect. Genetic factors accounted for the majority (62-77%) of this phenotypic association, although a significant proportion of this genetic covariation was due to genetic influences in common with negative affect. Nonshared environmental factors accounted for a relatively smaller (23-38%) proportion of the association, but these nonshared environmental effects were independent of negative affect. Findings suggest that the presence of emotion-based rash action, combined with high levels of negative affect, may significantly increase genetic risk for dysregulated eating. © 2013 American Psychological Association

Species differences in the negative inotropic effect of acetylcholine and soman in rat, guinea pig, and rabbit hearts. (Reannouncement with new availability information)

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

Maxwell, D.M.; Thomsen, R.H.; Baskin, S.I.

1991-12-31

Acetylcholine reduced atrial contractions by 82.5% in guinea pig, 50.8% in rat, and 41.5% in rabbit. 2. The EC50, values for the negative inotropic effect of acetylcholine were 3.3 x 10(-7) M in rat and guinea pig atria and 4.1 x 10(-6) M in rabbit atria. 3. There was no correlation between the species differences in the negative inotropic effect of acetylcholine in atria and the density or affinity of acetylcholinesterase or muscarinic receptors. 4. Inhibition of atrial acetylcholinesterase with soman reduced the EC50 of acetylcholine three-fold in all species, but did not change the maximal inotropic effect of acetylcholine.more » 5. Species differences in the negative inotropic effect of acetylcholine may be caused by differences in the coupling between myocardial muscarinic receptors and the ion channels that mediate negative inotropy. Acetylcholine, cardiovascular response, species variation negative inotropic response.« less

Manipulating affective state influences conditioned appetitive responses.

PubMed

Arnaudova, Inna; Krypotos, Angelos-Miltiadis; Effting, Marieke; Kindt, Merel; Beckers, Tom

2017-10-06

Affective states influence how individuals process information and behave. Some theories predict emotional congruency effects (e.g. preferential processing of negative information in negative affective states). Emotional congruency should theoretically obstruct the learning of reward associations (appetitive learning) and their ability to guide behaviour under negative mood. Two studies tested the effects of the induction of a negative affective state on appetitive Pavlovian learning, in which neutral stimuli were associated with chocolate (Experiment 1) or alcohol (Experiment 2) rewards. In both experiments, participants showed enhanced approach tendencies towards predictors of reward after a negative relative to a positive performance feedback manipulation. This increase was related to a reduction in positive affect in Experiment 1 only. No effects of the manipulation on conditioned reward expectancies, craving, or consumption were observed. Overall, our findings support the idea of counter-regulation, rather than emotional congruency effects. Negative affective states might therefore serve as a vulnerability factor for addiction, through increasing conditioned approach tendencies.

Further Investigating Method Effects Associated with Negatively Worded Items on Self-Report Surveys

ERIC Educational Resources Information Center

DiStefano, Christine; Motl, Robert W.

2006-01-01

This article used multitrait-multimethod methodology and covariance modeling for an investigation of the presence and correlates of method effects associated with negatively worded items on the Rosenberg Self-Esteem (RSE) scale (Rosenberg, 1989) using a sample of 757 adults. Results showed that method effects associated with negative item phrasing…

Commitment to Nonwork Roles and Job Performance: Enrichment and Conflict Perspectives

ERIC Educational Resources Information Center

Weer, Christy H.; Greenhaus, Jeffrey H.; Linnehan, Frank

2010-01-01

An extensive commitment to nonwork roles was negatively associated with the job performance of 182 women legal secretaries. In addition to its direct negative effect on job performance, nonwork role commitment had both a negative indirect effect (through emotional energy expended on nonwork roles) and a positive indirect effect (through resources…

Prosocial Behavior Mitigates the Negative Effects of Stress in Everyday Life

PubMed Central

Raposa, Elizabeth B.; Laws, Holly B.; Ansell, Emily B.

2015-01-01

Recent theories of stress reactivity posit that, when stressed, individuals tend to seek out opportunities to affiliate with and nurture others in order to prevent or mitigate the negative effects of stress. However, few studies have tested empirically the role of prosocial behavior in reducing negative emotional responses to stress. The current analyses used daily diary data to investigate whether engaging in prosocial behavior buffered the negative effects of naturally-occurring stressors on emotional well-being. Results showed that on a given day, prosocial behavior moderated the effects of stress on positive affect, negative affect, and overall mental health. Findings suggest that affiliative behavior may be an important component of coping with stress, and indicate that engaging in prosocial behavior might be an effective strategy for reducing the impact of stress on emotional functioning. PMID:27500075

Prosocial Behavior Mitigates the Negative Effects of Stress in Everyday Life.

PubMed

Raposa, Elizabeth B; Laws, Holly B; Ansell, Emily B

2016-07-01

Recent theories of stress reactivity posit that, when stressed, individuals tend to seek out opportunities to affiliate with and nurture others in order to prevent or mitigate the negative effects of stress. However, few studies have tested empirically the role of prosocial behavior in reducing negative emotional responses to stress. The current analyses used daily diary data to investigate whether engaging in prosocial behavior buffered the negative effects of naturally-occurring stressors on emotional well-being. Results showed that on a given day, prosocial behavior moderated the effects of stress on positive affect, negative affect, and overall mental health. Findings suggest that affiliative behavior may be an important component of coping with stress, and indicate that engaging in prosocial behavior might be an effective strategy for reducing the impact of stress on emotional functioning.

Sensitive Detection: Photoacoustics, Thermography, and Optical Radiation Pressure

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

Diebold, Gerald J.

Research during the granting period has been carried out in several areas concerned with sensitive detection. An infrared pyrometer based on the photoacoustic effect has been developed. The sensitivity of this instrument to temperature differentials has been shown to be 50 mK. An investigation of transients that accompany photoacoustic waves generated by pulsed lasers has been carried out. Experiments have shown the existence of the transients, and a theory based on rapid heat diffusion has been developed. The photoacoustic effect in one dimension is known to increase without bound (in the linear acoustics regime) when an optical beam moves inmore » a fluid at the sound speed. A solution to the wave equation for pressure has been found that describes the photoacoustic effect in a cell where an infrared optical grating moves at the sound speed. It was shown that the amplification effect exists along with a cavity resonance that can be used to great advantage in trace gas detection. The theory of the photoacoustic effect in a structure where the acoustic properties periodically vary in a one-dimensional based has been formulated based on solutions to a Mathieu equation. It was found that it is possible to excite photoacoustic waves within the band gaps to produce large amplitude acoustic waves. The idea of self-oscillation in a photoacoustic cell using a continuous laser has been investigated. A theory has been completed showing that in a compressive wave, the absorption increases as a result of the density increase leading to further absorption and hence an increased amplitude photoacoustic effect with the result that in a resonator, self-oscillation can place. Experiments have been carried out where irradiation of a suspension of absorbing carbon particles with a high power laser has been shown to result in cavitation luminescence. That is, following generation of CO and H 2 from the carbon particles through the carbon-steam reaction, an expanding gas bubble is produced, which during the phase where the bubble collapses, a sonoluminescent flash is produced. Work on the voltage generated by a spherical, colloidal object irradiated with an acoustic wave has been determined. The theory of X-ray imaging using a grating to generate a spatially heterodyned image has been formulated. The properties of X-ray images taken with a grating placed before the object and the resulting image Fourier transformed and filtered has been determined. The method essentially heterodynes the spatial component of the object in the image which can be used to eliminate scatter that degrades contrast. Another area of investigation is the motion of the components in a separation method known as thermal diffusion, or the Soret effect. By exploring the mathematics of the effect, it was found that the underlying mechanism of the separation is propagation of a shock whose features are masked typically by the effects of viscosity.« less

Gender, negative life events and coping on different stages of depression severity: A cross-sectional study among Chinese university students.

PubMed

Sun, Xiao-Jun; Niu, Geng-Feng; You, Zhi-Qi; Zhou, Zong-Kui; Tang, Yun

2017-02-01

The effects of gender, negative life events, and coping on depression have been well-documented. But depression is a heterogeneous syndrome of which the severity ranged from mild depression to major depression. This study aimed to investigate the specific effects of gender, negative life events, and coping on different stages of depression severity. A total of 5989 students (aged 16-25 years, M=20.85, SD=0.58), recruited from six universities in the central region of China using the stratified cluster sampling method, completed Life Events Questionnaire, Coping Response Inventory, and Beck Depression Inventory-Ⅱ. Among the participants, 708 (11.8%) students presented different severity levels of depression. Gender, negative life events, positive coping, and negative coping all had significant effects on depression. That is, the possibility of being depressed was significantly higher in female university students, or students who had more negative life events, more negative coping, or positive coping. In terms of the different stages of depression severity, all these factors had significant effects on the stage from non- depression to mild depression; only gender, negative life events and positive coping had significant effects on the stage from mild depression to moderate depression; only gender had a significant effect on the stage from moderate depression to major depression. The causal role of these factors on different stages of depression severity could not be inferred. Moreover, the participants were from a non-clinical population. The effects of gender, negative life events and coping varied in different stages of depression severity. The effects of life events and coping styles became insignificant with the increasing severity of depression, whereas the effect of gender remained significant. The results could provide guidance for the prevention, intervention, and treatment of depression. Copyright © 2016. Published by Elsevier B.V.

The therapeutic effect of negative pressure in treating femoral head necrosis in rabbits.

PubMed

Zhang, Yin-gang; Wang, Xuezhi; Yang, Zhi; Zhang, Hong; Liu, Miao; Qiu, Yushen; Guo, Xiong

2013-01-01

Because negative pressure can stimulate vascular proliferation, improve blood circulation and promote osteogenic differentiation of bone marrow stromal cells, we investigated the therapeutic effect of negative pressure on femoral head necrosis (FHN) in a rabbit model. Animals were divided into four groups (n = 60/group): [1] model control, [2] core decompression, [3] negative pressure and [4] normal control groups. Histological investigation revealed that at 4 and 8 weeks postoperatively, improvements were observed in trabecular bone shape, empty lacunae and numbers of bone marrow hematopoietic cells and fat cells in the negative pressure group compared to the core decompression group. At week 8, there were no significant differences between the negative pressure and normal control groups. Immunohistochemistry staining revealed higher expression of vascular endothelial growth factor (VEGF) and bone morphogenetic protein-2 (BMP-2) in the femoral heads in the negative pressure group compared with the core decompression group. Transmission electron microscopy revealed that cell organelles were further developed in the negative pressure group compared with the core decompression group. Microvascular ink staining revealed an increased number of bone marrow ink-stained blood vessels, a thicker vascular lumen and increased microvascular density in the negative pressure group relative to the core decompression group. Real-time polymerase chain reaction revealed that expression levels of both VEGF and BMP-2 were higher in the negative pressure group compared with the core decompression group. In summary, negative pressure has a therapeutic effect on FHN. This effect is superior to core decompression, indicating that negative pressure is a potentially valuable method for treating early FHN.

The Therapeutic Effect of Negative Pressure in Treating Femoral Head Necrosis in Rabbits

PubMed Central

Zhang, Yin-gang; Wang, Xuezhi; Yang, Zhi; Zhang, Hong; Liu, Miao; Qiu, Yushen; Guo, Xiong

2013-01-01

Because negative pressure can stimulate vascular proliferation, improve blood circulation and promote osteogenic differentiation of bone marrow stromal cells, we investigated the therapeutic effect of negative pressure on femoral head necrosis (FHN) in a rabbit model. Animals were divided into four groups (n = 60/group): [1] model control, [2] core decompression, [3] negative pressure and [4] normal control groups. Histological investigation revealed that at 4 and 8 weeks postoperatively, improvements were observed in trabecular bone shape, empty lacunae and numbers of bone marrow hematopoietic cells and fat cells in the negative pressure group compared to the core decompression group. At week 8, there were no significant differences between the negative pressure and normal control groups. Immunohistochemistry staining revealed higher expression of vascular endothelial growth factor (VEGF) and bone morphogenetic protein-2 (BMP-2) in the femoral heads in the negative pressure group compared with the core decompression group. Transmission electron microscopy revealed that cell organelles were further developed in the negative pressure group compared with the core decompression group. Microvascular ink staining revealed an increased number of bone marrow ink-stained blood vessels, a thicker vascular lumen and increased microvascular density in the negative pressure group relative to the core decompression group. Real-time polymerase chain reaction revealed that expression levels of both VEGF and BMP-2 were higher in the negative pressure group compared with the core decompression group. In summary, negative pressure has a therapeutic effect on FHN. This effect is superior to core decompression, indicating that negative pressure is a potentially valuable method for treating early FHN. PMID:23383276

Bidirectional-Compounding Effects of Rumination and Negative Emotion in Predicting Impulsive Behavior: Implications for Emotional Cascades.

PubMed

Selby, Edward A; Kranzler, Amy; Panza, Emily; Fehling, Kara B

2016-04-01

Influenced by chaos theory, the emotional cascade model proposes that rumination and negative emotion may promote each other in a self-amplifying cycle that increases over time. Accordingly, exponential-compounding effects may better describe the relationship between rumination and negative emotion when they occur in impulsive persons, and predict impulsive behavior. Forty-seven community and undergraduate participants who reported frequent engagement in impulsive behaviors monitored their ruminative thoughts and negative emotion multiple times daily for two weeks using digital recording devices. Hypotheses were tested using cross-lagged mixed model analyses. Findings indicated that rumination predicted subsequent elevations in rumination that lasted over extended periods of time. Rumination and negative emotion predicted increased levels of each other at subsequent assessments, and exponential functions for these associations were supported. Results also supported a synergistic effect between rumination and negative emotion, predicting larger elevations in subsequent rumination and negative emotion than when one variable alone was elevated. Finally, there were synergistic effects of rumination and negative emotion in predicting number of impulsive behaviors subsequently reported. These findings are consistent with the emotional cascade model in suggesting that momentary rumination and negative emotion progressively propagate and magnify each other over time in impulsive people, promoting impulsive behavior. © 2014 Wiley Periodicals, Inc.

Understanding the factors that determine registered nurses' turnover intentions.

PubMed

Osuji, Joseph; Uzoka, Faith-Michael; Aladi, Flora; El-Hussein, Mohammed

2014-01-01

Turnover among registered nurses (RNs) produces a negative impact on the health outcomes of any health care organization. It is also recognized universally as a problem in the nursing profession. Little is known about the turnover intentions and career orientations of RNs working in Calgary, Alberta, Canada. The aim of this study is to contribute to the knowledge of and to advance the discussion on the turnover of nursing professionals. The study population consisted of RNs employed in the five major hospitals in Calgary. There were 193 surveys returned, representing a response rate of 77.2%. The results show that age and education have a negative effect on turnover intention. Education was found to have a significant negative effect on career satisfaction but not on job satisfaction and organizational commitment. Length of service has a significant negative effect on turnover intention. Role ambiguity has significant highly negative effect on career satisfaction. Growth opportunity and supervisor support have a very significant positive effect on job satisfaction, career satisfaction, and organizational commitment. External career opportunities and organizational commitment do not seem to have a significant effect on turnover intention. Career satisfaction, on the other hand, had negative significant effects on turnover intention.

Optical absorption and electrical properties of MPc (M =Fe, Cu, Zn)-TCNQ interfaces for optoelectronic applications

NASA Astrophysics Data System (ADS)

Sánchez Vergara, M. E.; Medrano Gallardo, D.; Vera Estrada, I. L.; Jiménez Sandoval, O.

2018-04-01

This research is related to the growth and characterization of doped molecular semiconductor metallophthalocyanine-tetracyanoquinodimethane (MPc-TCNQ) films, with M = Fe, Zn, Cu. FT-IR and Raman spectroscopies were employed to study the chemical interactions taking place in the MPc-TCNQ films. XRD was carried out to determine the crystalline structure present in the samples, due to the facility of the MPcs to be in alpha and/or beta phases. The thin films were analized by SEM and UV-vis spectroscopy in order to study their morphological and optical properties. The absorption spectra recorded in the UV-Vis region for the deposited samples showed two bands, namely the Q and Soret bands. The absorption coefficient (α) and photon energy (hν) were calculated from the UV-vis spectra, to in turn determine the optic activation energy in each film and its semiconductor behavior. The values obtained for direct transitions due to the crystallinity of the films were: 1.2, 1.4 and 2 eV for FePc-TCNQ (MMFe), ZnPc-TCNQ (MMZn) and CuPc-TCNQ (MMCu), respectively. Additionally, I-V characteristics have been obtained from fabricated glass/ITO/MM/Ag devices using ohmic contacts both after annealing. The electrical properties of the devices, e.g. carrier mobility and concentration of thermally generated holes, were extracted from the J-V characteristics. The results show that the conduction process is ohmic for the MMZn and MMCu devices, at low voltages, while at high voltages, a space-charge-limited conduction (SCLC) is present. The effect of temperature on conductivity was also measured in these samples and the lower thermal activation energy calculated was 0.37 eV for MMZn. Moreover, it was found that the temperature-dependent electric current is always higher for the MMZn device and suggests a semiconductor-like behavior with an important conductivity of the order of 103 S cm-1. Anyhow, in terms not only of electric properties, but also of optic behavior, the results suggest that all three devices manufactured, MMFe, MMCu and MMZn, are of potential use in optoelectronics. The doping effect of TCNQ favors the electronic transport, most likely due to the formation of conduction channels caused by the anisotropy induced by the dopant.

Neural Correlates of Biased Responses: The Negative Method Effect in the Rosenberg Self-Esteem Scale Is Associated with Right Amygdala Volume.

PubMed

Wang, Yinan; Kong, Feng; Huang, Lijie; Liu, Jia

2016-10-01

Self-esteem is a widely studied construct in psychology that is typically measured by the Rosenberg Self-Esteem Scale (RSES). However, a series of cross-sectional and longitudinal studies have suggested that a simple and widely used unidimensional factor model does not provide an adequate explanation of RSES responses due to method effects. To identify the neural correlates of the method effect, we sought to determine whether and how method effects were associated with the RSES and investigate the neural basis of these effects. Two hundred and eighty Chinese college students (130 males; mean age = 22.64 years) completed the RSES and underwent magnetic resonance imaging (MRI). Behaviorally, method effects were linked to both positively and negatively worded items in the RSES. Neurally, the right amygdala volume negatively correlated with the negative method factor, while the hippocampal volume positively correlated with the general self-esteem factor in the RSES. The neural dissociation between the general self-esteem factor and negative method factor suggests that there are different neural mechanisms underlying them. The amygdala is involved in modulating negative affectivity; therefore, the current study sheds light on the nature of method effects that are related to self-report with a mix of positively and negatively worded items. © 2015 Wiley Periodicals, Inc.

A Comparative Study on the Effects of Negative Evidence and Enriched Input on Learning of Verb-Noun Collocations

ERIC Educational Resources Information Center

Okyar, Hatice; Yangin Eksi, Gonca

2017-01-01

This study compared the effectiveness of negative evidence and enriched input on learning the verb-noun collocations. There were 52 English as Foreign Language (EFL) learners in this research study and they were randomly assigned to the negative evidence or enriched input groups. While the negative evidence group (n = 27) was provided with…

Dependency, self-criticism and negative affective responses following imaginary rejection and failure threats: meaning-making processes as moderators or mediators.

PubMed

Besser, Avi; Priel, Beatriz

2011-01-01

This study evaluated the intervening role of meaning-making processes in emotional responses to negative life events based on Blatt's (1974, 2004) formulations concerning the role of personality predispositions in depression. In a pre/post within-subject study design, a community sample of 233 participants reacted to imaginary scenarios of interpersonal rejection and achievement failure. Meaning-making processes relating to threats to self-definition and interpersonal relatedness were examined following the exposure to the scenarios. The results indicated that the personality predisposition of Dependency, but not Self-Criticism predicted higher levels of negative affect following the interpersonal rejection event, independent of baseline levels of negative affect. This effect was mediated by higher levels of negative meaning-making processes related to the effect of the interpersonal rejection scenario on Dependent individuals' senses of interpersonal relatedness and self-worth. In addition, both Self-Criticism and Dependency predicted higher levels of negative affect following the achievement failure event, independent of baseline levels of negative affect. Finally, the effect of Self-Criticism was mediated by higher levels of negative meaning-making processes related to the effect of the achievement failure scenario on self-critical individuals' senses of self-definition.

Influence of negative emotion on the framing effect: evidence from event-related potentials.

PubMed

Ma, Qingguo; Pei, Guanxiong; Wang, Kai

2015-04-15

The framing effect is the phenomenon in which different descriptions of an identical problem can result in different choices. The influence of negative emotions on the framing effect and its neurocognitive basis are important issues, especially in the domain of saving lives, which is essential and highly risky. In each trial of our experiment, the emotion stimulus is presented to the participants, followed by the decision-making stimulus, which comprises certain and risky options with the same expected value. Each pair of options is positively or negatively framed. The behavioral results indicate a significant interactive effect between negative emotion and frame; thus, the risk preference under the positive frame can be enhanced by negative emotions, whereas this finding is not true under the negative frame. The event-related potential analysis indicates that choosing certain options under the positive frame with negative emotion priming generates smaller P2 and P3 amplitudes and a larger N2 amplitude than with neutral emotion priming. The event-related potential findings indicate that individuals can detect risk faster and experience more conflict and increased decision difficulty if they choose certain options under the positive frame with negative priming compared with neutral priming.

No fear, no panic: probing negation as a means for emotion regulation

PubMed Central

Deutsch, Roland; Platte, Petra; Pauli, Paul

2013-01-01

This electroencephalographic study investigated if negating one’s emotion results in paradoxical effects or leads to effective emotional downregulation. Healthy participants were asked to downregulate their emotions to happy and fearful faces by using negated emotional cue words (e.g. no fun, no fear). Cue words were congruent with the emotion depicted in the face and presented prior to each face. Stimuli were presented in blocks of happy and fearful faces. Blocks of passive stimulus viewing served as control condition. Active regulation reduced amplitudes of early event-related brain potentials (early posterior negativity, but not N170) and the late positive potential for fearful faces. A fronto-central negativity peaking at about 250 ms after target face onset showed larger amplitude modulations during downregulation of fearful and happy faces. Behaviorally, negating was more associated with reappraisal than with suppression. Our results suggest that in an emotional context, negation processing could be quite effective for emotional downregulation but that its effects depend on the type of the negated emotion (pleasant vs unpleasant). Results are discussed in the context of dual process models of cognition and emotion regulation. PMID:22490924

The effects of positive versus negative impact reflection on change in job performance and work-life conflict.

PubMed

Cardador, M Teresa

2014-01-01

Research on task significance and relational job design suggests that information from beneficiaries of one's work fosters perceptions of impact, and thus improved work outcomes. This paper presents results from a longitudinal field experiment examining the effect of another strategy for fostering perceptions of impact - engaging employees in regular reflection about how their work benefits others. With a sample of professionals from multiple organizations, this longitudinal study examined the effect on job performance and work-life conflict of both positive and negative impact reflection. Results show that negative impact reflection had a pronounced negative effect on job performance, but no effect on work-life conflict. Positive impact reflection had a weak positive effect on work-life conflict, but no significant effect on job performance. The direction of effects seen in the no intervention condition mirrored that of the negative impact reflection condition, suggesting a possible buffering effect for positive impact reflection. This research provides empirical and theoretical contributions to the literatures on relational job design and task significance.

The effects of positive versus negative impact reflection on change in job performance and work-life conflict

PubMed Central

Cardador, M. Teresa

2014-01-01

Research on task significance and relational job design suggests that information from beneficiaries of one’s work fosters perceptions of impact, and thus improved work outcomes. This paper presents results from a longitudinal field experiment examining the effect of another strategy for fostering perceptions of impact – engaging employees in regular reflection about how their work benefits others. With a sample of professionals from multiple organizations, this longitudinal study examined the effect on job performance and work-life conflict of both positive and negative impact reflection. Results show that negative impact reflection had a pronounced negative effect on job performance, but no effect on work-life conflict. Positive impact reflection had a weak positive effect on work-life conflict, but no significant effect on job performance. The direction of effects seen in the no intervention condition mirrored that of the negative impact reflection condition, suggesting a possible buffering effect for positive impact reflection. This research provides empirical and theoretical contributions to the literatures on relational job design and task significance. PMID:25505890

The effect of negative experiences on delinquent behavior of youth in a social withdrawal situation.

PubMed

Chan, Gloria Hongyee; Lo, T Wing

2016-07-01

This study examines the relationship between negative experiences, negative emotions, and delinquent behavior among young people in a social withdrawal situation. There were 533 participants in this study and various quantitative analyses were utilized. Results showed that participants with a longer period of social withdrawal were generally less affected by negative experiences, while those with a higher level of social withdrawal were more affected by negative experiences, particularly negative relationships with other people. Also, both negative emotions and higher level of social withdrawal mediated the relationship between negative experiences and involvement in delinquent behavior, with negative emotions displaying a higher mediating effect. This reflects that the root of delinquent behavior is the negative experiences which arouse negative emotions, rather than the social withdrawal behavior itself. Results imply that practitioners should first explore the negative experiences suffered by these young people, so as to provide them the most appropriate support. Copyright © 2016 The Foundation for Professionals in Services for Adolescents. Published by Elsevier Ltd. All rights reserved.

Emotion dysregulation explains the relation between insomnia symptoms and negative reinforcement smoking cognitions among daily smokers.

PubMed

Kauffman, Brooke Y; Farris, Samantha G; Alfano, Candice A; Zvolensky, Michael J

2017-09-01

Insomnia co-occurs with smoking. However, mechanisms that may explain their comorbidity are not well known. The present study tested the hypothesis that insomnia would exert an indirect effect on negative reinforcement smoking processes via emotion dysregulation among 126 adult non-treatment seeking daily smokers (55 females; M age =44.1years, SD=9.72). Negative reinforcement smoking processes included negative reinforcement smoking outcome expectancies, negative reinforcement smoking motives, and two negative expectancies from brief smoking abstinence (somatic symptoms and harmful consequences). Insomnia symptoms yielded a significant indirect effect through emotion dysregulation for negative reinforcement smoking outcome expectancies, negative reinforcement smoking motives, and harmful consequences expectancies from brief smoking abstinence. In contrast to prediction, however, insomnia was not associated with somatic symptom expectancies from brief smoking abstinence through emotion dysregulation. These data may suggest that the indirect effect of emotion dysregulation is more relevant to cognitive-affective negative reinforcement processes rather than somatic states. Overall, the present findings contribute to a growing body of literature linking emotion dysregulation as an explanatory mechanism for insomnia and smoking and uniquely extend such work to an array of clinically significant negative reinforcement smoking processes. Copyright © 2017 Elsevier Ltd. All rights reserved.

Saint-Venant end effects for materials with negative Poisson's ratios

NASA Technical Reports Server (NTRS)

Lakes, R. S.

1992-01-01

Results are presented from an analysis of Saint-Venant end effects for materials with negative Poisson's ratio. Examples are presented showing that slow decay of end stress occurs in circular cylinders of negative Poisson's ratio, whereas a sandwich panel containing rigid face sheets and a compliant core exhibits no anomalous effects for negative Poisson's ratio (but exhibits slow stress decay for core Poisson's ratios approaching 0.5). In sand panels with stiff but not perfectly rigid face sheets, a negative Poisson's ratio results in end stress decay, which is faster than it would be otherwise. It is suggested that the slow decay previously predicted for sandwich strips in plane deformation as a result of the geometry can be mitigated by the use of a negative Poisson's ratio material for the core.

Reconsolidation from negative emotional pictures: is successful retrieval required?

PubMed

Finn, Bridgid; Roediger, Henry L; Rosenzweig, Emily

2012-10-01

Finn and Roediger (Psychological science 22:781-786, 2011) found that when a negative emotional picture was presented immediately after a successful retrieval, later test performance was enhanced as compared to when a neutral picture or a blank screen had been shown. This finding implicates the period immediately following retrieval as playing an important role in determining later retention via reconsolidation. In two new experiments, we investigated whether successful retrieval was required to show the enhancing effect of negative emotion on later recall. In both experiments, the participants studied Swahili-English vocabulary pairs, took an intervening cued-recall test, and were given a final cued-recall test on all items. In Experiment 1, we tested a distinctiveness explanation of the effect. The results showed that neither presentation of a negative picture just prior to successful retrieval nor presentation of a positive picture after successful retrieval produced the enhancing effect that was seen when negative pictures were presented after successful retrieval. In Experiment 2, we tested whether the enhancing effect would occur when a negative picture followed an unsuccessful retrieval attempt with feedback, and a larger enhancement effect occurred after errors of commission than after errors of omission. These results indicate that effort in retrieving is critical to the enhancing effect shown with negative pictures; whether the target is produced by the participant or given by an external source following a commission error does not matter. We interpret these results as support for semantic enrichment as a key element in producing the enhancing effect of negative pictures that are presented after a retrieval attempt.

Positive smoking outcome expectancies mediate the association between negative affect and smoking urge among women during a quit attempt.

PubMed

Cano, Miguel Ángel; Lam, Cho Y; Chen, Minxing; Adams, Claire E; Correa-Fernández, Virmarie; Stewart, Diana W; McClure, Jennifer B; Cinciripini, Paul M; Wetter, David W

2014-08-01

Ecological momentary assessment was used to examine associations between negative affect, positive smoking outcome expectancies, and smoking urge during the first 7 days of a smoking quit attempt. Participants were 302 female smokers who enrolled in an individually tailored smoking cessation treatment study. Multilevel mediation analysis was used to examine the temporal relationship among the following: (a) the effects of negative affect and positive smoking outcome expectancies at 1 assessment point (e.g., time j) on smoking urge at the subsequent time point (e.g., time j + 1) in Model 1; and, (b) the effects of negative affect and smoking urge at time j on positive smoking outcome expectancies at time j + 1 in Model 2. The results from Model 1 showed a statistically significant effect of negative affect at time j on smoking urge at time j + 1, and this effect was mediated by positive smoking outcome expectancies at time j, both within- and between-participants. In Model 2, the within-participant indirect effect of negative affect at time j on positive smoking outcome expectancies at time j + 1 through smoking urge at time j was nonsignificant. However, a statistically significant indirect between-participants effect was found in Model 2. The findings support the hypothesis that urge and positive smoking outcome expectancies increase as a function of negative affect, and suggest a stronger effect of expectancies on urge as opposed to the effect of urge on expectancies.

Positive Smoking Outcome Expectancies Mediate the Association between Negative Affect and Smoking Urge among Women During a Quit Attempt

PubMed Central

Cano, Miguel Ángel; Lam, Cho Y.; Chen, Minxing; Adams, Claire E.; Correa-Fernández, Virmarie; Stewart, Diana W.; McClure, Jennifer B.; Cinciripini, Paul M.; Wetter, David W.

2014-01-01

Ecological momentary assessment was used to examine associations between negative affect, positive smoking outcome expectancies, and smoking urge during the first 7 days of a smoking quit attempt. Participants were 302 female smokers who enrolled in an individually tailored smoking cessation treatment study. Multilevel mediation analysis was used to examine the temporal relationship among: 1) the effects of negative affect and positive smoking outcome expectancies at one assessment point (e.g., time j) on smoking urge at the subsequent time point (e.g., time j + 1) in Model 1; and, 2) the effects of negative affect and smoking urge at time j on positive smoking outcome expectancies at time j + 1 in Model 2. The results from Model 1 showed a statistically significant effect of negative affect at time j on smoking urge at time j + 1, and this effect was mediated by positive smoking outcome expectancies at time j, both within- and between-participant. In Model 2, the within-participant indirect effect of negative affect at time j on positive smoking outcome expectancies at time j + 1 through smoking urge at time j was nonsignificant. However, a statistically significant indirect between-participant effect was found in Model 2. The findings support the hypothesis that urge and positive smoking outcome expectancies increase as a function of negative affect, and suggest a stronger effect of expectancies on urge as opposed to the effect of urge on expectancies. PMID:24796849

Indirect effect of financial strain on daily cortisol output through daily negative to positive affect index in the Coronary Artery Risk Development in Young Adults Study.

PubMed

Puterman, Eli; Haritatos, Jana; Adler, Nancy E; Sidney, Steve; Schwartz, Joseph E; Epel, Elissa S

2013-12-01

Daily affect is important to health and has been linked to cortisol. The combination of high negative affect and low positive affect may have a bigger impact on increasing HPA axis activity than either positive or negative affect alone. Financial strain may both dampen positive affect as well as increase negative affect, and thus provides an excellent context for understanding the associations between daily affect and cortisol. Using random effects mixed modeling with maximum likelihood estimation, we examined the relationship between self-reported financial strain and estimated mean daily cortisol level (latent cortisol variable), based on six salivary cortisol assessments throughout the day, and whether this relationship was mediated by greater daily negative to positive affect index measured concurrently in a sample of 776 Coronary Artery Risk Development in Young Adults (CARDIA) Study participants. The analysis revealed that while no total direct effect existed for financial strain on cortisol, there was a significant indirect effect of high negative affect to low positive affect, linking financial strain to elevated cortisol. In this sample, the effects of financial strain on cortisol through either positive affect or negative affect alone were not significant. A combined affect index may be a more sensitive and powerful measure than either negative or positive affect alone, tapping the burden of chronic financial strain, and its effects on biology. Copyright © 2013 Elsevier Ltd. All rights reserved.

Rotavirus vaccine effectiveness in low-income settings: An evaluation of the test-negative design.

PubMed

Schwartz, Lauren M; Halloran, M Elizabeth; Rowhani-Rahbar, Ali; Neuzil, Kathleen M; Victor, John C

2017-01-03

The test-negative design (TND), an epidemiologic method currently used to measure rotavirus vaccine (RV) effectiveness, compares the vaccination status of rotavirus-positive cases and rotavirus-negative controls meeting a pre-defined case definition for acute gastroenteritis. Despite the use of this study design in low-income settings, the TND has not been evaluated to measure rotavirus vaccine effectiveness. This study builds upon prior methods to evaluate the use of the TND for influenza vaccine using a randomized controlled clinical trial database. Test-negative vaccine effectiveness (VE-TND) estimates were derived from three large randomized placebo-controlled trials (RCTs) of monovalent (RV1) and pentavalent (RV5) rotavirus vaccines in sub-Saharan Africa and Asia. Derived VE-TND estimates were compared to the original RCT vaccine efficacy estimates (VE-RCTs). The core assumption of the TND (i.e., rotavirus vaccine has no effect on rotavirus-negative diarrhea) was also assessed. TND vaccine effectiveness estimates were nearly equivalent to original RCT vaccine efficacy estimates. Neither RV had a substantial effect on rotavirus-negative diarrhea. This study supports the TND as an appropriate epidemiologic study design to measure rotavirus vaccine effectiveness in low-income settings. Copyright © 2016 The Author(s). Published by Elsevier Ltd.. All rights reserved.

Immediate effects of chocolate on experimentally induced mood states.

PubMed

Macht, Michael; Mueller, Jochen

2007-11-01

In this work two hypotheses were tested: (1) that eating a piece of chocolate immediately affects negative, but not positive or neutral mood, and (2) that this effect is due to palatability. Experiment 1 (48 normal-weight and healthy women and men) examined the effects of eating a piece of chocolate and drinking water on negative, positive and neutral mood states induced by film clips. Eating chocolate reduced negative mood compared to drinking water, whereas no or only marginal effects were found on neutral and positive moods. Experiment 2 (113 normal-weight and healthy women and men) compared effects of eating palatable and unpalatable chocolate on negative mood, and examined the duration of chocolate-induced mood change. Negative mood was improved after eating palatable chocolate as compared to unpalatable chocolate or nothing. This effect was short lived, i.e., it disappeared after 3 min. In both experiments, chocolate-induced mood improvement was associated with emotional eating. The present studies demonstrate that eating a small amount of sweet food improves an experimentally induced negative mood state immediately and selectively and that this effect of chocolate is due to palatability. It is hypothesized that immediate mood effects of palatable food contribute to the habit of eating to cope with stress.

Meta-atom cluster acoustic metamaterial with broadband negative effective mass density

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

Chen, Huaijun; Zhai, Shilong; Ding, Changlin

2014-02-07

We design a resonant meta-atom cluster, via which a two-dimensional (2D) acoustic metamaterial (AM) with broadband negative effective mass density from 1560 Hz to 5580 Hz is fabricated. Experimental results confirm that there is only weak interaction among the meta-atoms in the cluster. And then the meta-atoms in the cluster independently resonate, resulting in the cluster becoming equivalent to a broadband resonance unit. Extracted effective refractive indices from reflection and transmission measurements of the 2D AM appear to be negative from 1500 Hz to 5480 Hz. The broadband negative refraction has also been demonstrated by our further experiments. We expectmore » that this meta-atom cluster AM will significantly contribute to the design of broadband negative effective mass density AM.« less

Mutual Influence of Reward Anticipation and Emotion on Brain Activity during Memory Retrieval.

PubMed

Yan, Chunping; Liu, Fang; Li, Yunyun; Zhang, Qin; Cui, Lixia

2017-01-01

Previous studies on the joint effect of reward motivation and emotion on memory retrieval have obtained inconsistent results. Furthermore, whether and how any such joint effect might vary over time remains unclear too. Accordingly, using the event-related potential (ERP) measurement of high temporal resolution, our study investigates the cognitive and brain mechanisms of monetary reward and emotion affecting the retrieval processes of episodic memory. Twenty undergraduate and graduate students participated in the research, and our study's behavioral results indicated that reward (relative to no reward) and negative emotion (relative to positive and neutral emotion) significantly improved recognition performance. The ERP results showed that there were significant interactions between monetary reward and emotion on memory retrieval, and the reward effects of positive, neutral, and negative memory occurred at varied intervals in mean amplitude. The reward effect of positive memory appeared relatively early, at 260-330 ms after the stimulus onset in the frontal-frontocentral area, at 260-500 ms in the centroparietal-parietal area and at 500-700 ms in the frontocentral area. However, the reward effects of neutral and negative memory occurred relatively later, and that of negative memory appeared at 500-700 ms in the frontocentral and centroparietal area and that of neutral memory was at 500-700 ms in the frontocentral and centroparietal-parietal area. Meanwhile, significant FN400 old/new effects were observed in the negative and rewarded positive items, and the old/new effects of negative items appeared earlier at FN400 than positive items. Also, significant late positive component (LPC) old/new effects were found in the positive, negative, and rewarded neutral items. These results suggest that, monetary reward and negative emotion significantly improved recognition performance, and there was a mutual influence between reward and emotion on brain activity during memory retrieval.

General Rule of Negative Effective Ueff System & Materials Design of High-Tc Superconductors by ab initio Calculations

NASA Astrophysics Data System (ADS)

Katayama-Yoshida, Hiroshi; Nakanishi, Akitaka; Uede, Hiroki; Takawashi, Yuki; Fukushima, Tetsuya; Sato, Kazunori

2014-03-01

Based upon ab initio electronic structure calculation, I will discuss the general rule of negative effective U system by (1) exchange-correlation-induced negative effective U caused by the stability of the exchange-correlation energy in Hund's rule with high-spin ground states of d5 configuration, and (2) charge-excitation-induced negative effective U caused by the stability of chemical bond in the closed-shell of s2, p6, and d10 configurations. I will show the calculated results of negative effective U systems such as hole-doped CuAlO2 and CuFeS2. Based on the total energy calculations of antiferromagnetic and ferromagnetic states, I will discuss the magnetic phase diagram and superconductivity upon hole doping. I also discuss the computational materials design method of high-Tc superconductors by ab initio calculation to go beyond LDA and multi-scale simulations.

[Negative symptoms of schizophrenia: from electrophysiology to electrotherapy].

PubMed

Micoulaud Franchi, J-A; Quiles, C; Belzeaux, R; Adida, M; Azorin, J-M

2015-12-01

The aim of this review of the literature is to summarize the state of the knowledge concerning the relationship between negative symptoms in schizophrenia, electrophysiology and electrotherapy. The scientific literature search of international articles was performed during August and September 2015 using the PubMed electronic database. We used the following MeSH terms: "Negative symptoms", "Schizophrenia", "Electrophysiology", "Neurophysiology", "EEG power", "Alpha rhythm", "Transcranial magnetic stimulation", "Transcranial direct current stimulation", "Electroconvulsive therapy", "Neurofeedback", "Vagus Nerve Stimulation", "Deep Brain Stimulation", and "State dependent". Negative symptoms in schizophrenia are associated with altered activity in prefrontal cortex in functional neuroimaging studies. This is in line with electrophysiological measurements that found a change in EEG spectral power in the alpha frequency band over prefrontal brain regions. The notion of functional hypofrontality has led to hypotheses that electrotherapy applied to the prefrontal cortex may be an effective treatment of negative symptoms in schizophrenia. Repetitive transcranial magnetic stimulation (rTMS) and transcranial direct current stimulation (tDCS) were used to increase cortical activity in schizophrenia and achieve a clinical effect on negative symptoms. Three meta-analyses confirmed, with a moderate effect size, that rTMS is an effective treatment option for negative symptoms in schizophrenia. The two subsequently published prospective multicenter studies, however, found opposite results from each other. Two randomized controlled studies suggested that tDCS is an effective treatment option for negative symptoms. There is no study on the efficacy of neurofeedback, vagal nerve stimulation or deep brain stimulation on negative symptoms in schizophrenia. Additional studies are needed to confirm the efficacy of rTMS and tDCS on negative symptoms in schizophrenia. Influencing factors, related to clinical and stimulation parameters, of rTMS and tDCS on negative symptoms should be better investigated. Effects related to electrophysiological brain activity of the patient, especially in the alpha band, during the stimulation should also be better investigated. The action of electrotherapy may be state dependent, and a better understanding of electrophysiological effects of electrotherapy techniques could enable their optimization. Copyright © 2015 Elsevier Masson SAS. All rights reserved.

Dose reduction of risperidone and olanzapine can improve cognitive function and negative symptoms in stable schizophrenic patients: A single-blinded, 52-week, randomized controlled study.

PubMed

Zhou, Yanling; Li, Guannan; Li, Dan; Cui, Hongmei; Ning, Yuping

2018-05-01

The long-term effects of dose reduction of atypical antipsychotics on cognitive function and symptomatology in stable patients with schizophrenia remain unclear. We sought to determine the change in cognitive function and symptomatology after reducing risperidone or olanzapine dosage in stable schizophrenic patients. Seventy-five stabilized schizophrenic patients prescribed risperidone (≥4 mg/day) or olanzapine (≥10 mg/day) were randomly divided into a dose-reduction group ( n=37) and a maintenance group ( n=38). For the dose-reduction group, the dose of antipsychotics was reduced by 50%; for the maintenance group, the dose remained unchanged throughout the whole study. The Positive and Negative Syndrome Scale, Negative Symptom Assessment-16, Rating Scale for Extrapyramidal Side Effects, and Measurement and Treatment Research to Improve Cognition in Schizophrenia (MATRICS) Consensus Cognitive Battery were measured at baseline, 12, 28, and 52 weeks. Linear mixed models were performed to compare the Positive and Negative Syndrome Scale, Negative Symptom Assessment-16, Rating Scale for Extrapyramidal Side Effects and MATRICS Consensus Cognitive Battery scores between groups. The linear mixed model showed significant time by group interactions on the Positive and Negative Syndrome Scale negative symptoms, Negative Symptom Assessment-16, Rating Scale for Extrapyramidal Side Effects, speed of processing, attention/vigilance, working memory and total score of MATRICS Consensus Cognitive Battery (all p<0.05). Post hoc analyses showed significant improvement in Positive and Negative Syndrome Scale negative subscale, Negative Symptom Assessment-16, Rating Scale for Extrapyramidal Side Effects, speed of processing, working memory and total score of MATRICS Consensus Cognitive Battery for the dose reduction group compared with those for the maintenance group (all p<0.05). This study indicated that a risperidone or olanzapine dose reduction of 50% may not lead to more severe symptomatology but can improve speed of processing, working memory and negative symptoms in patients with stabilized schizophrenia.

The Effect of Drawing Exercises on Mood When Negative Affect Is Not Induced

ERIC Educational Resources Information Center

Northcott, Jessica L.; Frein, Scott T.

2017-01-01

In this study we examined the effects of drawing on positive and negative affect, when negative mood induction is not used as has been done in prior research. There were 64 participants ranging in age from 18 to 24 who completed 1 of the following activities: drawing, writing, or sitting quietly for 10 min. Positive and negative affects were…

Different patterns of puberty effect in neural oscillation to negative stimuli: sex differences.

PubMed

Yuan, Jiajin; Ju, Enxia; Yang, Jiemin; Chen, Xuhai; Li, Hong

2014-12-01

The present study investigated the impact of puberty on sex differences in neural sensitivity to negative stimuli. Event-related oscillation technique was used. Because girls are more vulnerable to affective disturbances than boys during adolescence, it was hypothesized that puberty exerts different influences on neural sensitivity to negative stimuli in boys and girls. EEGs were recorded for highly negative (HN), mildly negative (MN) and neutral pictures, when boys and girls distinct in pubertal status performed a non-emotional distracting task. No emotion effect and its interaction with sex and puberty were observed in response latencies. However, puberty influenced the gamma-band oscillation effect for negative stimuli differently for boys and girls: Pre-pubertal boys showed a significant emotion effect for HN stimuli, whose size was decreased in pubertal boys. By contrast, there was a significant emotion effect for HN stimuli in pubertal girls but not in pre-pubertal girls. On the other hand, the size of the emotion effect for HN stimuli was similar for pre-pubertal boys and girls; while this effect was significantly more pronounced in pubertal girls compared to pubertal boys. Additionally, the size of the emotion effect in gamma oscillations decreased as a function of pubertal development during both HN and MN stimulation in boys. For girls, the emotion effect in gamma oscillations increased with pubertal development during HN stimulation. Thus, puberty is associated with reduced neural sensitivity in boys but increased sensitivity in girls, in reaction to negative stimuli. The implications of these results for the psychopathology during adolescence were discussed.

Field-induced phase transitions and enhanced double negative electrocaloric effects in (Pb,La)(Zr,Sn,Ti)O3 antiferroelectric single crystal

NASA Astrophysics Data System (ADS)

Zhuo, Fangping; Li, Qiang; Qiao, Huimin; Yan, Qingfeng; Zhang, Yiling; Xi, Xiaoqing; Chu, Xiangcheng; Long, Xifa; Cao, Wenwu

2018-03-01

Field-induced phase transitions and electrocaloric effect have been studied in (Pb,La)(Zr,Sn,Ti)O3 (PLZST) antiferroelectric single crystal. Temperature dependent dielectric, Raman spectra, as well as in situ domain evolution demonstrated that the order of phase transitions during heating is in the sequence of orthorhombic antiferroelectric → tetragonal antiferroelectric → cubic paraelectric. Enhanced negative electrocaloric effect value of -3.6 °C and electrocaloric strength of 0.3 K mm/kV at 125 °C have been achieved. Double negative effects (-0.7 °C at 45 °C and -3.6 °C at 125 °C) and a relatively large positive effect (1 °C) near Curie temperature (190 °C) have been found in the PLZST single crystal. Moreover, microscopic dipoles and a phenomenological Landau-type model were employed to understand these unusual electrocaloric effects. Enhanced negative effect and the coexistence of both negative and positive effects in one material are promising for us to develop practical solid-state cooling devices with high efficiency.

Effect of hysteretic and non-hysteretic negative capacitance on tunnel FETs DC performance

NASA Astrophysics Data System (ADS)

Saeidi, Ali; Jazaeri, Farzan; Stolichnov, Igor; Luong, Gia V.; Zhao, Qing-Tai; Mantl, Siegfried; Ionescu, Adrian M.

2018-03-01

This work experimentally demonstrates that the negative capacitance effect can be used to significantly improve the key figures of merit of tunnel field effect transistor (FET) switches. In the proposed approach, a matching condition is fulfilled between a trained-polycrystalline PZT capacitor and the tunnel FET (TFET) gate capacitance fabricated on a strained silicon-nanowire technology. We report a non-hysteretic switch configuration by combining a homojunction TFET and a negative capacitance effect booster, suitable for logic applications, for which the on-current is increased by a factor of 100, the transconductance by 2 orders of magnitude, and the low swing region is extended. The operation of a hysteretic negative capacitance TFET, when the matching condition for the negative capacitance is fulfilled only in a limited region of operation, is also reported and discussed. In this late case, a limited improvement in the device performance is observed. Overall, the paper demonstrates the main beneficial effects of negative capacitance on TFETs are the overdrive and transconductance amplification, which exactly address the most limiting performances of current TFETs.

Mindful attention predicts greater recovery from negative emotions, but not reduced reactivity.

PubMed

Cho, Sinhae; Lee, Hyejeen; Oh, Kyung Ja; Soto, José A

2017-09-01

This study investigated the role of dispositional mindful attention in immediate reactivity to, and subsequent recovery from, laboratory-induced negative emotion. One hundred and fourteen undergraduates viewed blocks of negative pictures followed by neutral pictures. Participants' emotional responses to negative pictures and subsequent neutral pictures were assessed via self-reported ratings. Participants' emotional response to negative pictures was used to index level of emotional reactivity to unpleasant stimuli; emotional response to neutral pictures presented immediately after the negative pictures was used to index level of emotional recovery from pre-induced negative emotion (residual negativity). Results indicated that mindful attention was not associated with the emotional response to negative pictures, but it was associated with reduced negative emotion in response to the neutral pictures presented immediately after the negative pictures, suggesting better recovery as opposed to reduced reactivity. This effect was especially pronounced in later experimental blocks when the accumulation of negative stimuli produced greater negative emotion from which participants had to recover. The current study extends previous findings on the relationship between dispositional mindfulness and reduced negative emotion by demonstrating that mindful attention may facilitate better recovery from negative emotion, possibly through more effective disengagement from previous stimuli.

Prediction of large negative shaded-side spacecraft potentials

NASA Technical Reports Server (NTRS)

Prokopenko, S. M. L.; Laframboise, J. G.

1977-01-01

A calculation by Knott, for the floating potential of a spherically symmetric synchronous-altitude satellite in eclipse, was adapted to provide simple calculations of upper bounds on negative potentials which may be achieved by electrically isolated shaded surfaces on spacecraft in sunlight. Large (approximately 60 percent) increases in predicted negative shaded-side potentials are obtained. To investigate effective potential barrier or angular momentum selection effects due to the presence of less negative sunlit-side or adjacent surface potentials, these expressions were replaced by the ion random current, which is a lower bound for convex surfaces when such effects become very severe. Further large increases in predicted negative potentials were obtained, amounting to a doubling in some cases.

Negative ion treatment increases positive emotional processing in seasonal affective disorder.

PubMed

Harmer, C J; Charles, M; McTavish, S; Favaron, E; Cowen, P J

2012-08-01

Antidepressant drug treatments increase the processing of positive compared to negative affective information early in treatment. Such effects have been hypothesized to play a key role in the development of later therapeutic responses to treatment. However, it is unknown whether these effects are a common mechanism of action for different treatment modalities. High-density negative ion (HDNI) treatment is an environmental manipulation that has efficacy in randomized clinical trials in seasonal affective disorder (SAD). The current study investigated whether a single session of HDNI treatment could reverse negative affective biases seen in seasonal depression using a battery of emotional processing tasks in a double-blind, placebo-controlled randomized study. Under placebo conditions, participants with seasonal mood disturbance showed reduced recognition of happy facial expressions, increased recognition memory for negative personality characteristics and increased vigilance to masked presentation of negative words in a dot-probe task compared to matched healthy controls. Negative ion treatment increased the recognition of positive compared to negative facial expression and improved vigilance to unmasked stimuli across participants with seasonal depression and healthy controls. Negative ion treatment also improved recognition memory for positive information in the SAD group alone. These effects were seen in the absence of changes in subjective state or mood. These results are consistent with the hypothesis that early change in emotional processing may be an important mechanism for treatment action in depression and suggest that these effects are also apparent with negative ion treatment in seasonal depression.

Fast and fragile: A new look at the automaticity of negation processing.

PubMed

Deutsch, Roland; Kordts-Freudinger, Robert; Gawronski, Bertram; Strack, Fritz

2009-01-01

Numerous studies suggest that processing verbal materials containing negations slows down cognition and makes it more error-prone. This suggests that processing negations affords relatively nonautomatic processes. The present research studied the role of two automaticity features (processing speed and resource dependency) for negation processing. In three experiments, we tested the impact of verbal negations on affective priming effects in the Affect Misattribution Paradigm. Going beyond previous work, the results indicate that negations can be processed unintentionally and quickly (Experiments 1 and 2). In Experiment 3, negations failed to qualify affective priming effects when participants' working memory was taxed by memorizing an eight-digit number. In sum, the experiments suggest that negations can be processed unintentionally, very quickly, but that they rely on working-memory resources.

Conspecific Leaf Litter-Mediated Effect of Conspecific Adult Neighborhood on Early-Stage Seedling Survival in A Subtropical Forest

PubMed Central

Liu, Heming; Shen, Guochun; Ma, Zunping; Yang, Qingsong; Xia, Jianyang; Fang, Xiaofeng; Wang, Xihua

2016-01-01

Conspecific adults have strong negative effect on the survival of nearby early-stage seedlings and thus can promote species coexistence by providing space for the regeneration of heterospecifics. The leaf litter fall from the conspecific adults, and it could mediate this conspecific negative adult effect. However, field evidence for such effect of conspecific leaf litter remains absent. In this study, we used generalized linear mixed models to assess the effects of conspecific leaf litter on the early-stage seedling survival of four dominant species (Machilus leptophylla, Litsea elongate, Acer pubinerve and Distylium myricoides) in early-stage seedlings in a subtropical evergreen broad-leaved forest in eastern China. Our results consistently showed that the conspecific leaf litter of three species negatively affected the seedling survival. Meanwhile, the traditional conspecific adult neighborhood indices failed to detect this negative conspecific adult effect. Our study revealed that the accumulation of conspecific leaf litter around adults can largely reduce the survival rate of nearby seedlings. Ignoring it could result in underestimation of the importance of negative density dependence and negative species interactions in the natural forest communities. PMID:27886275

Conspecific Leaf Litter-Mediated Effect of Conspecific Adult Neighborhood on Early-Stage Seedling Survival in A Subtropical Forest.

PubMed

Liu, Heming; Shen, Guochun; Ma, Zunping; Yang, Qingsong; Xia, Jianyang; Fang, Xiaofeng; Wang, Xihua

2016-11-25

Conspecific adults have strong negative effect on the survival of nearby early-stage seedlings and thus can promote species coexistence by providing space for the regeneration of heterospecifics. The leaf litter fall from the conspecific adults, and it could mediate this conspecific negative adult effect. However, field evidence for such effect of conspecific leaf litter remains absent. In this study, we used generalized linear mixed models to assess the effects of conspecific leaf litter on the early-stage seedling survival of four dominant species (Machilus leptophylla, Litsea elongate, Acer pubinerve and Distylium myricoides) in early-stage seedlings in a subtropical evergreen broad-leaved forest in eastern China. Our results consistently showed that the conspecific leaf litter of three species negatively affected the seedling survival. Meanwhile, the traditional conspecific adult neighborhood indices failed to detect this negative conspecific adult effect. Our study revealed that the accumulation of conspecific leaf litter around adults can largely reduce the survival rate of nearby seedlings. Ignoring it could result in underestimation of the importance of negative density dependence and negative species interactions in the natural forest communities.

Neonicotinoid insecticides negatively affect performance measures of non‐target terrestrial arthropods: a meta‐analysis

USGS Publications Warehouse

Main, Anson; Webb, Elisabeth B.; Goyne, Keith W.; Mengel, Doreen C.

2018-01-01

Neonicotinoid insecticides are currently the fastest‐growing and most widely used insecticide class worldwide. Valued for their versatility in application, these insecticides may cause deleterious effects in a range of non‐target (beneficial) arthropods. However, it remains unclear whether strong patterns exist in terms of their major effects, if broad measures of arthropod performance are negatively affected, or whether different functional groups are equally vulnerable. Here, we present a meta‐analysis of 372 observations from 44 field and laboratory studies that describe neonicotinoid effects on 14 arthropod orders across five broad performance measures: abundance, behavior, condition, reproductive success, and survival. Across studies, neonicotinoids negatively affected all performance metrics evaluated; however, magnitude of the effects varied. Arthropod behavior and survival were the most negatively affected and abundance was the least negatively affected. Effects on arthropod functional groups were inconsistent. Pollinator condition, reproductive success, and survival were significantly lower in neonicotinoid treatments compared to untreated controls; whereas, neonicotinoid effects on detritivores were not significant. Although magnitude of arthropod response to neonicotinoids varied among performance measures and functional groups, we documented a consistent negative relationship between exposure to neonicotinoid insecticides in published studies and beneficial arthropod performance.

Effects of age on negative subsequent memory effects associated with the encoding of item and item-context information.

PubMed

Mattson, Julia T; Wang, Tracy H; de Chastelaine, Marianne; Rugg, Michael D

2014-12-01

It has consistently been reported that "negative" subsequent memory effects--lower study activity for later remembered than later forgotten items--are attenuated in older individuals. The present functional magnetic resonance imaging study investigated whether these findings extend to subsequent memory effects associated with successful encoding of item-context information. Older (n = 25) and young (n = 17) subjects were scanned while making 1 of 2 encoding judgments on a series of pictures. Memory was assessed for the study item and, for items judged old, the item's encoding task. Both memory judgments were made using confidence ratings, permitting item and source memory strength to be unconfounded and source confidence to be equated across age groups. Replicating prior findings, negative item effects in regions of the default mode network in young subjects were reversed in older subjects. Negative source effects, however, were invariant with respect to age and, in both age groups, the magnitude of the effects correlated with source memory performance. It is concluded that negative item effects do not reflect processes necessary for the successful encoding of item-context associations in older subjects. Negative source effects, in contrast, appear to reflect the engagement of processes that are equally important for successful episodic encoding in older and younger individuals. © The Author 2013. Published by Oxford University Press. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

Fidelity Moderates the Association Between Negative Condom Attitudes and Outcome Behavior in an Evidence-Based Sexual Risk Reduction Intervention for Female Sex Workers.

PubMed

Pitpitan, Eileen V; Chavarin, Claudia V; Semple, Shirley J; Mendoza, Doroteo; Rodriguez, Carlos Magis; Staines, Hugo; Aarons, Gregory A; Patterson, Thomas L

2017-06-01

Intervention fidelity and participant-level variables, such as negative attitudes towards condoms, are important variables to consider in the successful implementation of evidence-based HIV prevention interventions. Mujer Segura is an intervention that has been shown to be efficacious at reducing condomless sex for female sex workers (FSWs) in Mexico [1]. We examined main effects of fidelity, negative condom attitudes, and their interaction on the effectiveness of the Mujer Segura intervention at reducing condomless sex at intervention follow-up. Of the FSWs recruited from 13 cities across Mexico, 528 participated in the Mujer Segura intervention. We measured negative condom attitudes at baseline (comprising of beliefs and outcome evaluations) and condomless sex with clients at baseline and 6-month follow-up. Fidelity was measured by a fidelity checklist completed by independent raters; the sum of potentially 43 total elements completed by the counselor constituted fidelity. Complete fidelity was found in only 15.1% (n = 73) of sessions. There was no significant main effect of intervention fidelity on condomless sex with clients at follow-up. There was a significant and positive main effect of negative condom attitudes and a significant two-way interaction. At lower levels of fidelity, negative condom attitudes predicted greater condomless sex acts, whereas at higher levels of fidelity, the effect of condom attitudes became weaker. The results also indicated that the interaction between negative condom attitudes and fidelity were driven primarily by negative condom beliefs, as opposed to negative condom outcome evaluations. Ensuring treatment fidelity in an HIV prevention intervention is particularly important when participants have negative attitudes towards condoms.

Longitudinal multilevel models of the big-fish-little-pond effect on academic self-concept: counterbalancing contrast and reflected-glory effects in Hong Kong schools.

PubMed

Marsh, H W; Kong, C K; Hau, K T

2000-02-01

Longitudinal multilevel path models (7,997 students, 44 high schools, 4 years) evaluated effects of school-average achievement and perceived school status on academic self-concept in Hong Kong, which has a collectivist culture with a highly achievement-segregated high school system. Consistent with a priori predictions based on the big-fish-little-pond effect (BFLPE), higher school-average achievements led to lower academic self-concepts (contrast effect), whereas higher perceived school status had a counterbalancing positive effect on self-concept (reflected-glory, assimilation effect). The negative BFLPE is the net effect of counterbalancing influences, stronger negative contrast effects, and weaker positive assimilation effects so that controlling perceived school status led to purer--and even more negative--contrast effects. Attending a school where school-average achievement is high simultaneously resulted in a more demanding basis of comparison for one's own accomplishments (the stronger negative contrast effect) and a source of pride (the weaker positive assimilation effect).

Elucidating the Role of the Proximal Cysteine Hydrogen Bonding Network in Ferric Cytochrome P450cam and corresponding mutants using Magnetic Circular Dichroism Spectroscopy†

PubMed Central

Galinato, Mary Grace I.; Spolitak, Tatyana; Ballou, David P.; Lehnert, Nicolai

2011-01-01

Although there has been extensive research on various Cytochrome P450s, especially Cyt P450cam, there is much to be learned about the mechanism of how its functional unit, a heme b ligated by an axial cysteine, is finely tuned for catalysis by its second coordination sphere. Here we study how the hydrogen bonding network affects the proximal cysteine and the Fe-S(Cys) bond in ferric Cyt P450cam. This is accomplished using low-temperature magnetic circular dichroism (MCD) spectroscopy on wild-type (wt) Cyt P450cam, and on the mutants Q360P (pure ferric high-spin at low temperature) and L358P with which the “Cys pocket” has been altered (by removing amino acids involved in the hydrogen bonding network), and Y96W (pure ferric low-spin). The MCD spectrum of Q360P reveals fourteen electronic transitions between 15200 and 31050 cm-1. Variable-temperature variable-field (VTVH) saturation curves were used to determine the polarizations of these electronic transitions, with respect to in-plane (xy) and out-of-plane (z) polarization relative to the heme. The polarizations, oscillator strengths, and TD-DFT calculations were then used to assign the observed electronic transitions. In the lower energy region, prominent bands at 15909 and 16919 cm-1 correspond to porphyrin (P) → Fe charge transfer (CT) transitions. The band at 17881 cm-1 has distinct sulfur S(π)→ Fe CT contributions. The Q band is observed as a pseudo A-term (derivative shape) at 18604 and 19539 cm-1. In the case of the Soret band, the negative component of the expected pseudo A-term is split into two features due to mixing with another π → π* and potentially a P → Fe CT excited state. These features are observed at 23731, 24859, and 25618 cm-1. Most importantly, the broad, prominent band at 28570 cm-1 is assigned to the S(σ)→ Fe CT transition, whose intensity is generated through a multitude of CT transitions with strong iron character. For wt, Q360P, and L358P, this band occurs at 28724, 28570, and 28620 cm-1, respectively. The small shift of this feature upon altering the hydrogen bonds to the proximal cysteine indicates that the role of the Cys pocket is not primarily for electronic fine tuning of the sulfur donor strength, but is more for stabilizing the proximal thiolate against external reactants (NO, O2, H3O+), and for properly positioning cysteine to coordinate to the iron center. This aspect is discussed in detail. PMID:21158478

Self-control and parental control mediate the relationship between negative emotions and emotional eating among adolescents.

PubMed

Zhu, Hong; Luo, Xingwei; Cai, Taisheng; Li, Zhihua; Liu, Wenli

2014-11-01

The study was conducted to simultaneously investigate the mediating effects of parental control and adolescents' self-control on the relationship between adolescents' negative emotions and emotional eating, and to determine pathways with the greatest effect among these variables. Negative emotions, emotional eating, parental control, and self-control were investigated in 594 high school students (average age=16.70, SD=1.09) in Changsha City, China. High levels of negative emotions and parental control and low levels of self-control were strongly related to high levels of emotional eating in adolescents. In addition to the direct relationship between negative emotions and emotional eating, there was a mediating effect observed through low self-control and high parental control. The mediational effect of parental control was non-significant in adolescent boys. Furthermore, negative emotions related to emotional eating through the effect of parental control on adolescents' self-control. The degree to which both mediators explained the relationship between negative emotions and emotional eating ranged from 52.6% to 66.8%, and self-control had a stronger mediational effect than did parental control. The results indicate that both self-control and parental control should be considered in designing preventative measures against emotional eating in adolescents. Adolescent self-control training could also assist in preventing emotional eating. Copyright © 2014 Elsevier Ltd. All rights reserved.

Suppressor Effects of Positive and Negative Religious Coping on Academic Burnout Among Korean Middle School Students.

PubMed

Noh, Hyunkyung; Chang, Eunbi; Jang, Yoojin; Lee, Ji Hae; Lee, Sang Min

2016-02-01

Statistical suppressor effects in prediction models can provide evidence of the interdependent relationship of independent variables. In this study, the suppressor effects of positive and negative religious coping on academic burnout were examined using longitudinal data. First, 388 middle school students reported their type of religion and use of positive and negative religious coping strategies. Four months later, they also reported their level of academic burnout. From structural equation modeling, significant suppressor effects were found among religious students. That is, the coefficients became larger when both positive and negative religious coping predicted academic burnout simultaneously, compared to when each religious coping predicted academic burnout alone. However, suppressor effects were not found among non-religious students.

The influence of presentation format on the "bigger is better" (BIB) effect.

PubMed

Bromgard, Gregg D; Trafimow, David; Silvera, David H

2013-04-01

Two experiments tested the "bigger is better" (BIB) effect, whereby bigger objects are perceived more favorably than smaller ones. In Experiment 1, participants directly compared pairs of objects and a strong BIB effect was obtained for both positively and negatively valenced stimuli. In Experiment 2, comparative and absolute evaluations were combined in a single experiment and the BIB effect was mediated for positively and negatively valenced stimuli. Taken in combination, the data support a complex hypothesis that pair-wise presentations induce a comparative process that causes a BIB effect. But when objects are evaluated separately, size and valence interact such that increased size evokes more positive ratings of positive objects and more negative ratings for negative objects.

Giant Negative Electrocaloric Effect in (Pb,La)(Zr,Sn,Ti)O3 Antiferroelectrics Near Room Temperature.

PubMed

Zhuo, Fangping; Li, Qiang; Gao, Jinghan; Ji, Yongjie; Yan, Qingfeng; Zhang, Yiling; Wu, Hong-Hui; Xi, Xiao-Qing; Chu, Xiangcheng; Cao, Wenwu

2018-04-11

(Pb 0.97 La 0.02 )(Zr x Sn 0.94- x Ti 0.06 )O 3 (PLZST) antiferroelectric ceramics with x = 0.75-0.90 have been fabricated and found to be a novel electrocaloric material system with a giant negative electrocaloric effect (Δ T = -11.5 K) and a large electrocaloric strength (|Δ T/Δ E| = 0.105 K cm kV -1 ) near room temperature. Additionally, the PLZST antiferroelectric ceramic also exhibits a large positive electrocaloric effect around the Curie temperature. The giant negative effect and the coexistence of both positive and negative electrocaloric effects in one material indicate a promising possibility to develop mid- to large-scale solid-state cooling devices with high efficiency.

Plant-soil feedback in East-African savanna trees.

PubMed

Rutten, Gemma; Prati, Daniel; Hemp, Andreas; Fischer, Markus

2016-02-01

Research in savannas has focused on tree-grass interactions, whereas tree species coexistence received little attention. A leading hypothesis to explain tree coexistence is the Janzen-Connell model, which proposes an accumulation of host-specific enemies, e.g., soil organisms. While it has been shown in several non-savanna case studies that seedlings dispersed away from the mother perform better than seedlings that stay close (home-away effect), few studies tested whether foreign seedling species can replace own seedlings under conspecific adults (replacement effect). Some studies additionally tested for negative effects of conspecific biota (conspecific effect) to demonstrate the accumulation of enemies. We tested these effects by reciprocally growing seedlings of four tree species on soil collected beneath adults of all species, with and without applying a soil sterilization treatment. We found negative home-away effects suggesting that dispersal is advantageous and negative replacement effects suggesting species replacement under adults. While negative conspecific effects indicate accumulated enemies, positive heterospecific effects indicate an accumulation of mutualists rather than enemies for some species. We suggest that plant-soil feedbacks may well contribute to tree coexistence in savannas due to both negative conspecific and positive heterospecific feedbacks.

Positive fantasies or negative contrasts: the effect of media body ideals on restrained eaters' mood, weight satisfaction, and food intake.

PubMed

Boyce, Jessica A; Kuijer, Roeline G; Gleaves, David H

2013-09-01

Although viewing media body ideals promotes body dissatisfaction and problematic eating among women (e.g., extreme restraint/overeating), some argue that women only report such negative effects because they think that they are meant to (i.e., demand characteristics). Because restrained eaters are trying to lose weight, they might be vulnerable to such media exposure. However, because of demand characteristics, evidence is mixed. Therefore, we minimized demand characteristics and explored whether media body ideals would trigger restrained eaters to report negative (negative mood, weight dissatisfaction) or positive (positive mood, weight satisfaction) effects. We also hypothesized that this change (negative or positive) would encourage food intake. Restrained and unrestrained eaters (n=107) memorized media or control images. Restrained eaters exposed to media images reported decreased weight satisfaction and increased negative mood, but their food intake was not significantly affected. Perhaps paying advertent attention to the images caused goal-related negative affect, which triggered restraint. Copyright © 2013 Elsevier Ltd. All rights reserved.

Oxidation of hydroxylamine by cytochrome P-460 of the obligate methylotroph Methylococcus capsulatus Bath.

PubMed Central

Zahn, J A; Duncan, C; DiSpirito, A A

1994-01-01

An enzyme capable of the oxidation of hydroxylamine to nitrite was isolated from the obligate methylotroph Methylococcus capsulatus Bath. The absorption spectra in cell extracts, electron paramagnetic resonance spectra, molecular weight, covalent attachment of heme group to polypeptide, and enzymatic activities suggest that the enzyme is similar to cytochrome P-460, a novel iron-containing protein previously observed only in Nitrosomonas europaea. The native and subunit molecular masses of the M. capsulatus Bath protein were 38,900 and 16,390 Da, respectively; the isoelectric point was 6.98. The enzyme has approximately one iron and one copper atom per subunit. The electron paramagnetic resonance spectrum of the protein showed evidence for a high-spin ferric heme. In contrast to the enzyme from N. europaea, a 13-nm blue shift in the soret band of the ferrocytochrome (463 nm in cell extracts to 450 nm in the final sample) occurred during purification. The amino acid composition and N-terminal amino acid sequence of the enzyme from M. capsulatus Bath was similar but not identical to those of cytochrome P-460 of N. europaea. In cell extracts, the identity of the biological electron acceptor is as yet unestablished. Cytochrome c-555 is able to accept electrons from cytochrome P-460, although the purified enzyme required phenazine methosulfate for maximum hydroxylamine oxidation activity (specific activity, 366 mol of O2 per s per mol of enzyme). Hydroxylamine oxidation rates were stimulated approximately 2-fold by 1 mM cyanide and 1.5-fold by 0.1 mM 8-hydroxyquinoline. Images PMID:7928947

Lipid bilayer-coated mesoporous silica nanoparticles carrying bovine hemoglobin towards an erythrocyte mimic.

PubMed

Tu, Jing; Bussmann, Jeroen; Du, Guangsheng; Gao, Yue; Bouwstra, Joke A; Kros, Alexander

2018-05-30

Hemoglobin (Hb)-loaded mesoporous silica nanoparticles (MSNs) coated with a lipid bilayer (LB-MSNs) were investigated as an erythrocyte mimic. MSNs with a large average pore size (10 nm) act as a rigid core and provide a protective environment for Hb encapsulated inside the pores. The colloidal stability of Hb-loaded MSNs was enhanced upon the application of a lipid bilayer, through fusion of PEGylated liposomes onto the exterior surface of Hb-loaded MSNs. The morphology and mesostructure of the MSNs were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and surface area analysis. The Hb loading capacity (mg/g) in MSNs was studied by thermogravimetric analysis (TGA). UV-Vis absorption spectroscopy revealed that Hb inside MSNs had an identical, but slightly broadened peak in the Soret region compared to free Hb. Furthermore the encapsulated Hb exhibits similar peroxidase-like activity in catalyzing the oxidation of 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS) with hydrogen peroxide. The introduction of a supported lipid bilayer (LB) demonstrated the potential to prevent premature Hb release (the burst release decreased from 25.50 ± 0.33% to 6.73 ± 0.83%) and increased the colloidal stability of the Hb-loaded MSNs (hydrodynamic diameter remained ∼250 nm for at least one week). The in vivo systemic circulation and biodistribution of LB-MSNs were studied in optically transparent zebrafish embryos, revealing that LB-MSNs have the potential to act as an erythrocyte mimic in transfusion therapy. Copyright © 2018 Elsevier B.V. All rights reserved.

Characterization of structure and activity of garlic peroxidase (POX(1B)).

PubMed

El Ichi, Sarra; Miodek, Anna; Sauriat-Dorizon, Hélène; Mahy, Jean-Pierre; Henry, Céline; Marzouki, Mohamed Nejib; Korri-Youssoufi, Hafsa

2011-01-01

Structural characterization and study of the activity of new POX(1B) protein from garlic which has a high peroxidase activity and can be used as a biosensor for the detection of hydrogen peroxide and phenolic compounds were performed and compared with the findings for other heme peroxidases. The structure-function relationship was investigated by analysis of the spectroscopic properties and correlated to the structure determined by a new generation of high-performance hybrid mass spectrometers. The reactivity of the enzyme was analyzed by studies of the redox activity toward various ligands and the reactivity with various substrates. We demonstrated that, in the case of garlic peroxidase, the heme group is pentacoordinated, and has an histidine as a proximal ligand. POX(1B) exhibited a high affinity for hydrogen peroxide as well as various reducing cosubstrates. In addition, high enzyme specificity was demonstrated. The k(cat) and K(M) values were 411 and 400 mM(-1) s(-1) for 3,3',5,5'-tetramethylbenzidine and 2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid), respectively. Furthermore, the reduction of nitro compounds in the presence of POX(1B) was demonstrated by iron(II) nitrosoalkane complex assay. In addition, POX(1B) showed a great potential for application for drug metabolism since its ability to react with 1-nitrohexane in the presence of sodium dithionite was demonstrated by the appearance of a characteristic Soret band at 411 nm. The high catalytic efficiency obtained in the case of the new garlic peroxidase (POX(1B)) is suitable for the monitoring of different analytes and biocatalysis.

Purification and site-directed mutagenesis of linoleate 9S-dioxygenase-allene oxide synthase of Fusarium oxysporum confirms the oxygenation mechanism.

PubMed

Chen, Yang; Jernerén, Fredrik; Oliw, Ernst H

2017-07-01

Plants and fungi form jasmonic acid from α-linolenic acid. The first two steps of biosynthesis in plants occur by sequential transformation by 13S-lipoxygenase and allene oxide synthase (AOS). The biosynthesis in fungi may follow this classical scheme, but the only fungal AOS discovered so far are cytochromes P450 (CYP) fused to 8- and 9-dioxygenases (DOX). In the present report, we purified recombinant 9S-DOX-AOS of Fusarium oxysporum from cell lysate by cobalt affinity chromatography to near homogeneity and studied key residues by site-directed mutagenesis. Sequence homology with 8R-DOX-linoleate diol synthases (8R-DOX-LDS) suggested that Tyr414 catalyzes hydrogen abstraction and that Cys1051 forms the heme thiolate ligand. Site-directed mutagenesis (Tyr414Phe; Cys1051Ser) led to loss of 9S-DOX and 9S-AOS activities, respectively, but other important residues in the CYP parts of 5,8- and 7,8-LDS or 9R-AOS were not conserved. The UV-visible spectrum of 9S-DOX-AOS showed a Soret band at 409 nm, which shifted to 413 nm in the Cys1051Ser mutant. The 9S-AOS of the Tyr414Phe mutant transformed 9S-hydroperoxides of α-linolenic and linoleic acids to allene oxides/α-ketols, but it did not transform 13-hydroperoxides. We conclude that 9S- and 8R-DOX catalyze hydrogen abstraction at C-11 and C-8, respectively, by homologous Tyr residues. Copyright © 2017 Elsevier Inc. All rights reserved.

3-compartment talaporfin sodium pharmacokinetic model by optimization using fluorescence measurement data from canine skin to estimate the concentration in interstitial space

NASA Astrophysics Data System (ADS)

Uno, Yuko; Ogawa, Emiyu; Aiyoshi, Eitaro; Arai, Tsunenori

2018-02-01

We constructed the 3-compartment talaporfin sodium pharmacokinetic model for canine by an optimization using the fluorescence measurement data from canine skin to estimate the concentration in the interstitial space. It is difficult to construct the 3-compartment model consisted of plasma, interstitial space, and cell because there is a lack of the dynamic information. Therefore, we proposed the methodology to construct the 3-compartment model using the measured talaporfin sodium skin fluorescence change considering originated tissue part by a histological observation. In a canine animal experiment, the talaporfin sodium concentration time history in plasma was measured by a spectrophotometer with a prepared calibration curve. The time history of talaporfin sodium Q-band fluorescence on left femoral skin of a beagle dog excited by talaporfin sodium Soret-band of 409 nm was measured in vivo by our previously constructed measurement system. The measured skin fluorescence was classified to its source, that is, specific ratio of plasma, interstitial space, and cell. We represented differential rate equations of the talaporfin sodium concentration in plasma, interstitial space, cell. The specific ratios and a converting constant to obtain absolute value of skin concentration were arranged. Minimizing the squared error of the difference between the measured fluorescence data and calculated concentration by the conjugate gradient method in MATLAB, the rate constants in the 3-compartment model were determined. The accuracy of the fitting operation was confirmed with determination coefficient of 0.98. We could construct the 3-compartment pharmacokinetic model for canine using the measured talaporfin sodium fluorescence change from canine skin.

Investigating the Concept of Using Airglow Measurements to Detect Seismicity on Venus

NASA Astrophysics Data System (ADS)

Kenda, Balthasar; Lognonné, Philippe; Komjathy, Attila; Banerdt, Bruce; Cutts, Jim; Soret, Lauriane; Jackson, Jennifer

2017-04-01

The internal structure and dynamics of Venus are poorly constrained by observations. Seismology is among the best candidates for probing the interior of the planet, and it would also provide indispensable information about the present-day tectonic activity of Venus. However, due to the extreme surface temperatures, a long-duration seismic station seems to be beyond the technical capabilities achievable today. Nonetheless, the thick and dense atmosphere, which strongly couples with the ground, gives rise to the attractive option of detecting seismic waves from quakes within the atmosphere itself (Garcia et al., 2005, Lognonné and Johnson, 2007, 2015) using in-situ or remote-sensing measurements (Cutts et al., 2015). Here, we consider the bright airglow emission of O2 at 1.27 μm on the nightside of Venus and we model the intensity fluctuations induced by Venus quakes. Synthetic seismograms in the airglow layer, at 90-120 km altitude, are computed using normal-mode summation for a fully coupled solid planet-atmosphere system, including the effects of molecular relaxation of CO2 and a radiative boundary condition at the top of the atmosphere (Lognonné et al., 2016). The corresponding variations in the volumetric emission rate, calculated for realistic background intensities of the airglow (Soret et al., 2012), are then vertically integrated to reproduce the signals that would be seen from orbit. The noise level of existing airglow cameras suggests that the Rayleigh waves generated by quakes of magnitude 5 and above occurring on the nightside of the planet may be detectable up to about 60° in epicentral distance. A significant advantage of this technique is that a single orbiting camera may be sufficient to serve the role of a seismic network. By identifying and tracking the waves it is indeed possible to locate the source, estimate the magnitude and measure the horizontal surface-wave propagation velocities on Venus. In particular, it is expected that this would significantly constrain seismicity on Venus and, through the analysis of Rayleigh-wave dispersion, the structure of the crust and upper mantle.

Saddle-shaped porphyrins for dye-sensitized solar cells: new insight into the relationship between nonplanarity and photovoltaic properties.

PubMed

Shahroosvand, Hashem; Zakavi, Saeed; Sousaraei, Ahmad; Eskandari, Mortaza

2015-03-07

We report on the theoretical and experimental studies of the new dye-sensitized solar cells functionalized with 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin zinc(II) complexes bearing 2- and 8-bromo substituents at the β positions. In agreement with the results of TD-DFT calculations, the absorption maxima of di- and octa-brominated Zn(II) complexes, ZnTCPPBr2 and ZnTCPPBr8, exhibited large red-shift compared to that of the non-brominated free base porphyrin (H2TCPP). Furthermore, DFT calculations showed that the higher stabilization of the LUMO levels relative to the HOMO ones makes the HOMO-LUMO gap of the brominated Zn-porphyrins models smaller compared to that of the nonbrominated counterparts, which explains the red shifts of the Soret and Q bands of the brominated compounds. Solar cells containing the new saddle-shaped Zn(II) porphyrins were subjected to analysis in a photovoltaic calibration laboratory to determine their solar to electric energy conversion. In this regard, we found that the overall conversion efficiency of ZnTCPPBr8 adsorbed on TiO2 nanocrystalline films was 5 times as large as that of ZnTCPPBr2 adsorbed on the same films. The effect of the increasing number of Br groups on the photovoltaic performance of the complexes was compared to the results of computational methods using ab initio DFT molecular dynamics simulations and quantum dynamics calculations of electronic relaxation to investigate the interfacial electron transfer (IET) in TCPPBrx/TiO2-anatase nanostructures. Better IET in ZnTCPPBr8 compared to ZnTCPPBr2, and in H2TCPP was evaluated from interfacial electron transfer (IET) simulations. The IET results indicate that electron injection in ZnTCPPBr8-TiO2 (τ = 25 fs) can be up to 5 orders of magnitude faster than ZnTCPPBr2-TiO2 (τ = 125 fs). Both experimental and theoretical results demonstrate that the increase of the number of bromo-substituents at the β-pyrrole positions of the porphyrin macrocycle created a new class of porphyrin-based DSSC, which exhibits a remarkable increase in the photovoltaic performance compared to non-brominated porphyrins.

On ternary species mixing and combustion in isotropic turbulence at high pressure

NASA Astrophysics Data System (ADS)

Lou, Hong; Miller, Richard S.

2004-05-01

Effects of Soret and Dufour cross-diffusion, whereby both concentration and thermal diffusion occur in the presence of mass fraction, temperature, and pressure gradients, are investigated in the context of both binary and ternary species mixing and combustion in isotropic turbulence at large pressure. The compressible flow formulation is based on a cubic real-gas state equation, and includes generalized forms for heat and mass diffusion derived from nonequilibrium thermodynamics and fluctuation theory. A previously derived formulation of the generalized binary species heat and mass fluxes is first extended to the case of ternary species, and appropriate treatment of the thermal and mass diffusion factors is described. Direct numerical simulations (DNS) are then conducted for both binary and ternary species mixing and combustion in stationary isotropic turbulence. Mean flow temperatures and pressures of =700 K and =45 atm are considered to ensure that all species mixtures remain in the supercritical state such that phase changes do not occur. DNS of ternary species systems undergoing both pure mixing and a simple chemical reaction of the form O2+N2→2NO are then conducted. It is shown that stationary scalar states previously observed for binary mixing persist for the ternary species problem as well; however, the production and magnitude of the scalar variance is found to be altered for the intermediate molecular weight species as compared to the binary species case. The intermediate molecular weight species produces a substantially smaller scalar variance than the remaining species for all flows considered. For combustion of nonstoichiometric mixtures, a binary species mixture, characterized by stationary scalar states, results at long times after the lean reactant is depleted. The form of this final scalar distribution is observed to be similar to that found in the binary flow situation. A series of lower resolution simulations for a variety of species is then used to show the dependence of the stationary scalar variance on the turbulence Reynolds number, turbulence Mach number, species molecular weight ratio, and relative proportion of two species present in the flow after completion of combustion.

Four-Component Damped Density Functional Response Theory Study of UV/Vis Absorption Spectra and Phosphorescence Parameters of Group 12 Metal-Substituted Porphyrins.

PubMed

Fransson, Thomas; Saue, Trond; Norman, Patrick

2016-05-10

The influences of group 12 (Zn, Cd, Hg) metal-substitution on the valence spectra and phosphorescence parameters of porphyrins (P) have been investigated in a relativistic setting. In order to obtain valence spectra, this study reports the first application of the damped linear response function, or complex polarization propagator, in the four-component density functional theory framework [as formulated in Villaume et al. J. Chem. Phys. 2010 , 133 , 064105 ]. It is shown that the steep increase in the density of states as due to the inclusion of spin-orbit coupling yields only minor changes in overall computational costs involved with the solution of the set of linear response equations. Comparing single-frequency to multifrequency spectral calculations, it is noted that the number of iterations in the iterative linear equation solver per frequency grid-point decreases monotonously from 30 to 0.74 as the number of frequency points goes from one to 19. The main heavy-atom effect on the UV/vis-absorption spectra is indirect and attributed to the change of point group symmetry due to metal-substitution, and it is noted that substitutions using heavier atoms yield small red-shifts of the intense Soret-band. Concerning phosphorescence parameters, the adoption of a four-component relativistic setting enables the calculation of such properties at a linear order of response theory, and any higher-order response functions do not need to be considered-a real, conventional, form of linear response theory has been used for the calculation of these parameters. For the substituted porphyrins, electronic coupling between the lowest triplet states is strong and results in theoretical estimates of lifetimes that are sensitive to the wave function and electron density parametrization. With this in mind, we report our best estimates of the phosphorescence lifetimes to be 460, 13.8, 11.2, and 0.00155 s for H2P, ZnP, CdP, and HgP, respectively, with the corresponding transition energies being equal to 1.46, 1.50, 1.38, and 0.89 eV.

The consequences of perceived discrimination for psychological well-being: a meta-analytic review.

PubMed

Schmitt, Michael T; Branscombe, Nyla R; Postmes, Tom; Garcia, Amber

2014-07-01

In 2 meta-analyses, we examined the relationship between perceived discrimination and psychological well-being and tested a number of moderators of that relationship. In Meta-Analysis 1 (328 independent effect sizes, N = 144,246), we examined correlational data measuring both perceived discrimination and psychological well-being (e.g., self-esteem, depression, anxiety, psychological distress, life satisfaction). Using a random-effects model, the mean weighted effect size was significantly negative, indicating harm (r = -.23). Effect sizes were larger for disadvantaged groups (r = -.24) compared to advantaged groups (r = -.10), larger for children compared to adults, larger for perceptions of personal discrimination compared to group discrimination, and weaker for racism and sexism compared to other stigmas. The negative relationship was significant across different operationalizations of well-being but was somewhat weaker for positive outcomes (e.g., self-esteem, positive affect) than for negative outcomes (e.g., depression, anxiety, negative affect). Importantly, the effect size was significantly negative even in longitudinal studies that controlled for prior levels of well-being (r = -.15). In Meta-Analysis 2 (54 independent effect sizes, N = 2,640), we examined experimental data from studies manipulating perceptions of discrimination and measuring well-being. We found that the effect of discrimination on well-being was significantly negative for studies that manipulated general perceptions of discrimination (d = -.25), but effects did not differ from 0 when attributions to discrimination for a specific negative event were compared to personal attributions (d = .06). Overall, results support the idea that the pervasiveness of perceived discrimination is fundamental to its harmful effects on psychological well-being. PsycINFO Database Record (c) 2014 APA, all rights reserved.

Negative Priming in Free Recall Reconsidered

PubMed Central

2015-01-01

Negative priming in free recall is the finding of impaired memory performance when previously ignored auditory distracters become targets of encoding and retrieval. This negative priming has been attributed to an aftereffect of deploying inhibitory mechanisms that serve to suppress auditory distraction and minimize interference with learning and retrieval of task-relevant information. In 6 experiments, we tested the inhibitory account of the effect of negative priming in free recall against alternative accounts. We found that ignoring auditory distracters is neither sufficient nor necessary to produce the effect of negative priming in free recall. Instead, the effect is more readily accounted for by a buildup of proactive interference occurring whenever 2 successively presented lists of words are drawn from the same semantic category. PMID:26595066

The power of positive and negative expectations to influence reported symptoms and mood during exposure to wind farm sound.

PubMed

Crichton, Fiona; Dodd, George; Schmid, Gian; Gamble, Greg; Cundy, Tim; Petrie, Keith J

2014-12-01

Wind farm developments have been hampered by claims that sound from wind turbines causes symptoms and negative health reports in nearby residents. As scientific reviews have failed to identify a plausible link between wind turbine sound and health effects, psychological expectations have been proposed as an explanation for health complaints. Building on recent work showing negative expectations can create symptoms from wind turbines, we investigated whether positive expectations can produce the opposite effect, in terms of a reduction in symptoms and improvements in reported health. 60 participants were randomized to either positive or negative expectation groups and subsequently exposed to audible wind farm sound and infrasound. Prior to exposure, negative expectation participants watched a DVD incorporating TV footage about health effects said to be caused by infrasound produced by wind turbines. In contrast, positive expectation participants viewed a DVD that outlined the possible therapeutic effects of infrasound exposure. During exposure to audible windfarm sound and infrasound, symptoms and mood were strongly influenced by the type of expectations. Negative expectation participants experienced a significant increase in symptoms and a significant deterioration in mood, while positive expectation participants reported a significant decrease in symptoms and a significant improvement in mood. The study demonstrates that expectations can influence symptom and mood reports in both positive and negative directions. The results suggest that if expectations about infrasound are framed in more neutral or benign ways, then it is likely reports of symptoms or negative effects could be nullified.

Differential Effects of Positive versus Negative Self-Involving Counselor Responses.

ERIC Educational Resources Information Center

Remer, Pam; And Others

1983-01-01

Investigated the effects of positive and negative counselor disclosure using typescripts of hypothetical counseling interviews. Results indicated impact of condition was mixed, with each having some desirable effects. (PAS)

Ironic effects of emotion suppression when recounting distressing memories.

PubMed

Dalgleish, Tim; Yiend, Jenny; Schweizer, Susanne; Dunn, Barnaby D

2009-10-01

Theories of ironic mental control posit that under conditions in which effortful control is compromised, for example, in laboratory manipulations of mental load or in those suffering from clinical levels of negative affect, attempts to suppress negative emotions can lead to a paradoxical increase in such feelings, relative to conditions in which no suppression is attempted. In line with this, we showed that high negative affect participants, when asked to suppress (downregulate) their negative feelings while writing about a distressing personal memory, exhibited an ironically greater increase in negative emotions compared with a no-instruction condition, in contrast to low negative affect controls who were able to suppress their emotions. Comparable ironic effects were not associated with instructions to experience emotions. This first demonstration of ironic effects of emotion suppression in response to personal material in those with emotional problems sheds light into how certain emotion regulation strategies may maintain and exacerbate such conditions.

Child Temperament Moderates Effects of Parent-Child Mutuality on Self-Regulation: A Relationship-Based Path for Emotionally Negative Infants

PubMed Central

Kim, Sanghag; Kochanska, Grazyna

2012-01-01

This study examined infants’ negative emotionality as moderating the effect of parent-child Mutually Responsive Orientation (MRO) on children’s self-regulation (N=102). Negative emotionality was observed in anger-eliciting episodes and in interactions with parents at 7 months. MRO was coded in naturalistic interactions at 15 months. Self-regulation was measured at 25 months in effortful control battery and as self-regulated compliance to parental requests and prohibitions. Negative emotionality moderated the effects of mother-child MRO. Highly negative infants were less self-regulated when they were in unresponsive relationships (low MRO), but more self-regulated when in responsive relationships (high MRO). For infants not prone to negative emotionality, there was no link between MRO and self-regulation. The “regions-of-significance” analysis supported the differential susceptibility model not the diathesis-stress model. PMID:22670684

Specific and non-specific match effects in negative priming.

PubMed

Labossière, Danielle I; Leboe-McGowan, Jason P

2018-01-01

The negative priming effect occurs when withholding a response to a stimulus impairs generation of subsequent responding to a same or a related stimulus. Our goal was to use the negative priming procedure to obtain insights about the memory representations generated by ignoring vs. attending/responding to a prime stimulus. Across three experiments we observed that ignoring a prime stimulus tends to generate higher identity-independent, non-specific repetition effects, owing to an overlap in the coarse perceptual form of a prime distractor and a probe target. By contrast, attended repetition effects generate predominantly identity-specific sources of facilitation. We use these findings to advocate for using laboratory phenomena to illustrate general principles that can be of practical use to non-specialists. In the case of the negative priming procedure, we propose that the procedure provides a useful means for investigating attention/memory interactions, even if the specific cause (or causes) of negative priming effects remain unresolved. Copyright © 2017 Elsevier B.V. All rights reserved.

The Role of Negative Affect and Self-Concept Clarity in Predicting Self-Injurious Urges in Borderline Personality Disorder Using Ecological Momentary Assessment.

PubMed

Scala, J Wesley; Levy, Kenneth N; Johnson, Benjamin N; Kivity, Yogev; Ellison, William D; Pincus, Aaron L; Wilson, Stephen J; Newman, Michelle G

2018-01-01

Deficits in identity as well as negative affect have been shown to predict self-injurious and suicidal behaviors in individuals with borderline personality disorder (BPD). However, less is known about the interactive effects of these two predictors. We examined the moderating effect of a particular component of identity, self-concept, on the relationship between negative affect and self-injurious urges utilizing ecological momentary assessments. Outpatients diagnosed with either BPD (n = 36) or any anxiety disorder but no BPD (n = 18) completed surveys throughout the day over a 21-day period. Higher levels of momentary negative affect predicted greater subsequent urges to self-injure, but only when self-concept clarity was low (z = -3.60, p < .01). This effect did not differ between diagnostic groups. The results suggest that self-concept clarity has a protective effect against self-injurious urges in light of high negative affect, and that this effect may be transdiagnostic.

The polarizing effect of arousal on negotiation.

PubMed

Brown, Ashley D; Curhan, Jared R

2013-10-01

In this research, we examined the impact of physiological arousal on negotiation outcomes. Conventional wisdom and the prescriptive literature suggest that arousal should be minimized given its negative effect on negotiations, whereas prior research on misattribution of arousal suggests that arousal might polarize outcomes, either negatively or positively. In two experiments, we manipulated arousal and measured its effect on subjective and objective negotiation outcomes. Our results support the polarization effect. When participants had negative prior attitudes toward negotiation, arousal had a detrimental effect on outcomes, whereas when participants had positive prior attitudes toward negotiation, arousal had a beneficial effect on outcomes. These effects occurred because of the construal of arousal as negative or positive affect, respectively. Our findings have important implications not only for negotiation, but also for research on misattribution of arousal, which previously has focused on the target of evaluation, in contrast to the current research, which focused on the critical role of the perceiver.

Participation in HIV Behavioral Research: Unanticipated Benefits and Burdens.

PubMed

Tross, Susan; Pinho, Veronica; Lima, Jennifer E; Ghiroli, Megan; Elkington, Katherine S; Strauss, David H; Wainberg, Milton L

2018-04-30

HIV behavioral research has provided an invaluable knowledge base for effective approaches to behavioral challenges along the HIV care cascade. Little attention has been paid to tracking unanticipated effects of research participation, whether negative or positive. We used qualitative methods to elicit impressions of unanticipated effects of participation in behavioral research. An instrument was developed and piloted to assess positive (emotional gains, practical gains, HIV prevention knowledge and skills gains) and negative (emotional stress, discomfort with research) unanticipated effects. Participants (N = 25) from five projects, including men who have sex with men, adults who use substances, and youth, reported multiple positive unanticipated effects (sexual and drug risk reduction, goal setting, improvements in self-esteem and mood, relationship gains, health care behavior gains, knowledge and introspection gains) and rare unanticipated negative effects. Developing a systematic tool of unanticipated positive and negative effects of participation in behavioral research is a crucial next step.

Effects of Process and Outcome Accountability on Idea Generation.

PubMed

Häusser, Jan Alexander; Frisch, Johanna Ute; Wanzel, Stella; Schulz-Hardt, Stefan

2017-07-01

Previous research on the effects of outcome and process accountability on decision making has neglected the preceding phase of idea generation. We conducted a 2 (outcome accountability: yes vs. no) × 2 (process accountability: yes vs. no) experiment (N = 147) to test the effects of accountability on quantity and quality of generated ideas in a product design task. Furthermore, we examined potential negative side effects of accountability (i.e., stress and lengthened decision making). We found that (a) outcome accountability had a negative effect on quantity of ideas and (b) process accountability extended the idea generation process. Furthermore, any type of accountability (c) had a negative effect on uniqueness of ideas, (d) did not affect the quality of the idea that was selected, and (e) increased stress. Moreover, the negative effect of accountability on uniqueness of ideas was mediated by stress.

Does Negative Interaction in the Church Increase Psychological Distress? Longitudinal Findings from the Presbyterian Panel Survey*

PubMed Central

Ellison, Christopher G.; Zhang, Wei; Krause, Neal; Marcum, John P.

2009-01-01

This study examines the effects of negative interaction in church on psychological distress. After outlining a series of theoretical arguments linking negative interaction with health and well-being, relevant hypotheses are tested using longitudinal data from two surveys of the 1997–1999 Presbyterian Panel, a nationwide panel of members and elders (lay leaders) in congregations of the Presbyterian Church (USA). Findings confirm that negative interaction appears to foster or exacerbate distress over the study period. In addition, specific dimensions of social negativity have distinctive effects; the impact of criticisms on distress surface only in cross-sectional models, while the effects of excessive demands emerge only in the longitudinal models. No subgroup variations in these effects are detected. Implications of these findings are discussed with regard to (a) research on religion and health and (b) congregational life, and a number of promising directions for future research are elaborated. PMID:20694051

The implicit influence of a negative mood on the subliminal mere exposure effect.

PubMed

Kawakami, Naoaki

2012-12-01

Despite numerous studies on the mere exposure effect, it is still not clear why it occurs. The present study examined whether a negative mood would enhance or inhibit the effects. Fifty-two participants (30 men, 22 women; M age = 20.5 yr.) were assigned to one of two mood-induction groups (negative and neutral), and were exposed to a photograph 20 times after the mood induction. Thereafter, a single-category Implicit Association Test was conducted to measure their implicit attitudes toward the photograph. There was a significant interaction, with exposed stimuli evaluated more favorably than unexposed stimuli in the neutral condition, but not in the negative condition. This result suggests that a negative mood inhibited the mere exposure effect, implying that people could use their emotional states as cues to evaluate ambiguous objects that they have been repeatedly exposed to.

Testing the Interactive Effect of Parent and Child ADHD on Parenting in Mothers and Fathers: A Further Test of the Similarity-Fit Hypothesis

ERIC Educational Resources Information Center

Psychogiou, Lamprini; Daley, Dave; Thompson, Margaret; Sonuga-Barke, Edmund

2007-01-01

Mother and child ADHD symptoms both have a negative effect on parenting. Little is known about how these characteristics interact. In a recent paper, we reported two studies that suggested that maternal ADHD ameliorated the negative effects of child ADHD on negative parenting supporting a "similarity-fit" hypothesis. The aim of the current paper…

Electronic Cigarette Expectancies in Smokers with Psychological Distress.

PubMed

Miller, Mollie E; Tidey, Jennifer W; Rohsenow, Damaris J; Higgins, Stephen T

2017-01-01

Very few studies have evaluated perceptions of electronic nicotine delivery systems (ENDS) among smokers with mental illness. This study assessed expectancies about the effects of smoking combustible cigarettes or using ENDS among current smokers with and without severe psychological distress (SPD). We used a crowdsourcing system to survey 268 smokers on their expectancies for the effects of combustible cigarettes and ENDS. Positive expectancies assessed included negative affect reduction, stimulation, positive social effects and weight control, and negative expectancies included negative physical effects, negative psychosocial effects and future health concerns. Smokers with SPD had higher positive expectancies for weight control and social effects of both products compared to those without such distress, and higher expectancies for stimulation from combustible cigarettes compared to ENDS. All participants had significantly lower negative expectancies for ENDS compared to combustible cigarettes, with no significant differences between the groups. Smokers with SPD may be more vulnerable toward ENDS use, as they are for combustible cigarette use, due to greater positive expectancies of the products. Challenging positive expectancies may increase the efficacy of tobacco control efforts in this vulnerable population.

Electronic Cigarette Expectancies in Smokers with Psychological Distress

PubMed Central

Miller, Mollie E.; Tidey, Jennifer W.; Rohsenow, Damaris J.; Higgins, Stephen T.

2017-01-01

Objectives Very few studies have evaluated perceptions of electronic nicotine delivery systems (ENDS) among smokers with mental illness. This study assessed expectancies about the effects of smoking combustible cigarettes or using ENDS among current smokers with and without severe psychological distress (SPD). Methods We used a crowdsourcing system to survey 268 smokers on their expectancies for the effects of combustible cigarettes and ENDS. Positive expectancies assessed included negative affect reduction, stimulation, positive social effects and weight control, and negative expectancies included negative physical effects, negative psychosocial effects and future health concerns. Results Smokers with SPD had higher positive expectancies for weight control and social effects of both products compared to those without such distress, and higher expectancies for stimulation from combustible cigarettes compared to ENDS. All participants had significantly lower negative expectancies for ENDS compared to combustible cigarettes, with no significant differences between the groups. Conclusions Smokers with SPD may be more vulnerable toward ENDS use, as they are for combustible cigarette use, due to greater positive expectancies of the products. Challenging positive expectancies may increase the efficacy of tobacco control efforts in this vulnerable population. PMID:28653023

Practicing psychotherapists are more skilled at downregulating negative emotions than other professionals.

PubMed

Pletzer, Jan Luca; Sanchez, Xavier; Scheibe, Susanne

2015-09-01

Laypeople and psychotherapists alike tend to assume that psychotherapists are more effective than the average population in regulating negative emotions. Being receptive to patients' distress and being able to downregulate negative emotions are important skills for psychotherapists to provide effective help and sustain their own well-being. We investigated whether psychotherapists react to negative material differently and downregulate emotions more effectively than individuals working in other, nontherapeutic, professions. Practicing psychotherapists (n = 21) and a control group of nontherapists (n = 18) were exposed to pictures designed to elicit negative emotions in varying intensities and were asked to rate their emotional response, first after viewing them naturally and then after choosing and applying one of two given regulation strategies (i.e., distraction and reappraisal). Both groups responded similarly in terms of emotional reactivity and strategy choices, but psychotherapists were more effective than nontherapists in reducing their emotional response after applying emotion regulation strategies. We suggest that psychotherapists' comparable emotional reactivity and more effective emotion regulation make them well prepared to provide effective help to patients and safeguard their own well-being. (c) 2015 APA, all rights reserved).

Mutual Influence of Reward Anticipation and Emotion on Brain Activity during Memory Retrieval

PubMed Central

Yan, Chunping; Liu, Fang; Li, Yunyun; Zhang, Qin; Cui, Lixia

2017-01-01

Previous studies on the joint effect of reward motivation and emotion on memory retrieval have obtained inconsistent results. Furthermore, whether and how any such joint effect might vary over time remains unclear too. Accordingly, using the event-related potential (ERP) measurement of high temporal resolution, our study investigates the cognitive and brain mechanisms of monetary reward and emotion affecting the retrieval processes of episodic memory. Twenty undergraduate and graduate students participated in the research, and our study’s behavioral results indicated that reward (relative to no reward) and negative emotion (relative to positive and neutral emotion) significantly improved recognition performance. The ERP results showed that there were significant interactions between monetary reward and emotion on memory retrieval, and the reward effects of positive, neutral, and negative memory occurred at varied intervals in mean amplitude. The reward effect of positive memory appeared relatively early, at 260–330 ms after the stimulus onset in the frontal-frontocentral area, at 260–500 ms in the centroparietal-parietal area and at 500–700 ms in the frontocentral area. However, the reward effects of neutral and negative memory occurred relatively later, and that of negative memory appeared at 500–700 ms in the frontocentral and centroparietal area and that of neutral memory was at 500–700 ms in the frontocentral and centroparietal-parietal area. Meanwhile, significant FN400 old/new effects were observed in the negative and rewarded positive items, and the old/new effects of negative items appeared earlier at FN400 than positive items. Also, significant late positive component (LPC) old/new effects were found in the positive, negative, and rewarded neutral items. These results suggest that, monetary reward and negative emotion significantly improved recognition performance, and there was a mutual influence between reward and emotion on brain activity during memory retrieval. PMID:29118728

Positive messaging promotes walking in older adults

PubMed Central

Notthoff, Nanna; Carstensen, Laura L.

2014-01-01

Walking is among the most cost-effective and accessible means of exercise. Mounting evidence suggests that walking may help to maintain physical and cognitive independence in old age by preventing a variety of health problems. However, older Americans fall far short of meeting the daily recommendations for walking. In two studies, we examined whether considering older adults’ preferential attention to positive information may effectively enhance interventions aimed at promoting walking. In Study 1, we compared the effectiveness of positive, negative, and neutral messages to encourage walking (as measured with pedometers). Older adults who were informed about the benefits of walking walked more than those who were informed about the negative consequences of failing to walk, whereas younger adults were unaffected by framing valence. In Study 2, we examined within-person change in walking in older adults in response to positively- or negatively-framed messages over a 28-day period. Once again, positively-framed messages more effectively promoted walking than negatively-framed messages, and the effect was sustained across the intervention period. Together, these studies suggest that consideration of age-related changes in preferences for positive and negative information may inform the design of effective interventions to promote healthy lifestyles. Future research is needed to examine the mechanisms underlying the greater effectiveness of positively as opposed to negatively framed messages and the generalizability of findings to other intervention targets and other subpopulations of older adults. PMID:24956001

Aberration of a negative ion beam caused by space charge effect.

PubMed

Miyamoto, K; Wada, S; Hatayama, A

2010-02-01

Aberrations are inevitable when the charged particle beams are extracted, accelerated, transmitted, and focused with electrostatic and magnetic fields. In this study, we investigate the aberration of a negative ion accelerator for a neutral beam injector theoretically, especially the spherical aberration caused by the negative ion beam expansion due to the space charge effect. The negative ion current density profiles with the spherical aberration are compared with those without the spherical aberration. It is found that the negative ion current density profiles in a log scale are tailed due to the spherical aberration.

Negative refraction and planar focusing based on parity-time symmetric metasurfaces.

PubMed

Fleury, Romain; Sounas, Dimitrios L; Alù, Andrea

2014-07-11

We introduce a new mechanism to realize negative refraction and planar focusing using a pair of parity-time symmetric metasurfaces. In contrast to existing solutions that achieve these effects with negative-index metamaterials or phase conjugating surfaces, the proposed parity-time symmetric lens enables loss-free, all-angle negative refraction and planar focusing in free space, without relying on bulk metamaterials or nonlinear effects. This concept may represent a pivotal step towards loss-free negative refraction and highly efficient planar focusing by exploiting the largely uncharted scattering properties of parity-time symmetric systems.

Could the negative effects of static stretching in warm-up be restored by sport specific exercise?

PubMed

Bengtsson, Victor; Yu, Ji-Guo; Gilenstam, Kajsa

2017-04-13

Static stretching (SS) is widely used in warm-up as it is generally believed to increase mobility and reduce the risk of injury; however, SS has been shown to induce transient negative effects on subsequent muscle performance. Interestingly, recent studies have shown that sport specific exercise could restore SS-induced negative effects on certain sports, especially of explosive muscular performance. Whether sport specific exercise could restore SS-induced negative effects on isokinetic muscle performance remains unclear. The present study conducted two different warm-ups: 2-component warm-up and 3-component warm-up on 15 university students. Both protocols contained low intensity aerobic exercise and sport specific exercise, whereas the 3-component warm-up also contained SS which has been previously proven to induce negative effects on subsequent muscle performance. After the warm-ups, the subjects performed an isokinetic test on a Biodex. To make the sport specific exercise mimic the subsequent test, both included concentric isokinetic knee extension. During the tests, muscle performance of peak torque, mean power, and total work was recorded. Comparison of the measurements on each parameter between the two warm-ups was performed using paired t test. The comparisons did not reveal any significant difference in the measurement of any parameter between the two different warm-up protocols, and calculation of Cohen's revealed small effect sizes on all of the three variables. On basis of the present results and that the SS could induce transient negative effects on subsequent muscle performance, we concluded that the negative effects of the SS on the variables were restored by the isokinetic contractions.

Differential interference effects of negative emotional states on subsequent semantic and perceptual processing

PubMed Central

Gorlick, Marissa A.; Mather, Mara

2012-01-01

Past studies have revealed that encountering negative events interferes with cognitive processing of subsequent stimuli. The present study investigated whether negative events affect semantic and perceptual processing differently. Presentation of negative pictures produced slower reaction times than neutral or positive pictures in tasks that require semantic processing, such as natural/man-made judgments about drawings of objects, commonness judgments about objects, and categorical judgments about pairs of words. In contrast, negative picture presentation did not slow down judgments in subsequent perceptual processing (e.g., color judgments about words, and size judgments about objects). The subjective arousal level of negative pictures did not modulate the interference effects on semantic/perceptual processing. These findings indicate that encountering negative emotional events interferes with semantic processing of subsequent stimuli more strongly than perceptual processing, and that not all types of subsequent cognitive processing are impaired by negative events. PMID:22142207

Monoamine Oxidase A (MAOA) Genotype Predicts Greater Aggression Through Impulsive Reactivity to Negative Affect

PubMed Central

Chester, David S.; DeWall, C. Nathan; Derefinko, Karen J.; Estus, Steven; Peters, Jessica R.; Lynam, Donald R.; Jiang, Yang

2015-01-01

Low functioning MAOA genotypes have been reliably linked to increased reactive aggression, yet the psychological mechanisms of this effect remain largely unknown. The low functioning MAOA genotype’s established link to diminished inhibition and greater reactivity to conditions of negative affect suggest that negative urgency, the tendency to act impulsively in the context of negative affect, may fill this mediating role. Such MAOA carriers may have higher negative urgency, which may in turn predict greater aggressive responses to provocation. To test these hypotheses, 277 female and male participants were genotyped for an MAOA SNP yet to be linked to aggression (rs1465108), and then reported their negative urgency and past aggressive behavior. We replicated the effect of the low functioning MAOA genotype on heightened aggression, which was mediated by greater negative urgency. These results suggest that disrupted serotonergic systems predispose individuals towards aggressive behavior by increasing impulsive reactivity to negative affect. PMID:25637908

Differential interference effects of negative emotional states on subsequent semantic and perceptual processing.

PubMed

Sakaki, Michiko; Gorlick, Marissa A; Mather, Mara

2011-12-01

Past studies have revealed that encountering negative events interferes with cognitive processing of subsequent stimuli. The present study investigates whether negative events affect semantic and perceptual processing differently. Presentation of negative pictures produced slower reaction times than neutral or positive pictures in tasks that require semantic processing, such as natural or man-made judgments about drawings of objects, commonness judgments about objects, and categorical judgments about pairs of words. In contrast, negative picture presentation did not slow down judgments in subsequent perceptual processing (e.g., color judgments about words, size judgments about objects). The subjective arousal level of negative pictures did not modulate the interference effects on semantic or perceptual processing. These findings indicate that encountering negative emotional events interferes with semantic processing of subsequent stimuli more strongly than perceptual processing, and that not all types of subsequent cognitive processing are impaired by negative events. (c) 2011 APA, all rights reserved.

The amphetamine response moderates the relationship between negative emotionality and alcohol use.

PubMed

Allen, Kenneth J D; Gabbay, Frances H

2013-02-01

Considerable evidence suggests that sensitivity to the stimulant effects of alcohol and other drugs is a risk marker for heavy or problematic use of those substances. A separate body of research implicates negative emotionality. The goal of the present study was to evaluate the independent and interactive effects of the stimulant response, assessed with an amphetamine challenge, and negative emotionality on alcohol and drug use. Healthy young women and men completed the Multidimensional Personality Questionnaire (MPQ) and an inventory assessing alcohol and other drug use. Subsequently, the effects of 10-mg d-amphetamine were determined in the laboratory using the Stimulant scale of the Biphasic Alcohol Effects Scale. Hierarchical regression analyses evaluated the effects of amphetamine response and the MPQ factor Negative Emotionality on measures of substance use. The amphetamine response moderated relationships between negative emotionality and alcohol use: in combination with a robust amphetamine response (i.e., enhanced stimulant effects as compared with baseline), negative emotionality predicted greater alcohol consumption, more episodes of binge drinking, and more frequent intoxication in regression models. A strong stimulant response independently predicted having used an illicit drug, and there was a trend for it to predict having used alcohol. Negative emotionality alone was not associated with any measure of alcohol or drug use. Consistent with the idea that emotion-based behavioral dysregulation promotes reward seeking, a high level of negative emotionality was associated with maladaptive alcohol use when it co-occurred with sensitivity to drug-based reward. The findings contribute to our understanding of how differences in personality may interact with those in drug response to affect alcohol use. Copyright © 2012 by the Research Society on Alcoholism.

The amphetamine response moderates the relationship between negative emotionality and alcohol use

PubMed Central

Allen, Kenneth J. D.; Gabbay, Frances H.

2012-01-01

Background Considerable evidence suggests that sensitivity to the stimulant effects of alcohol and other drugs is a risk marker for heavy or problematic use of those substances. A separate body of research implicates negative emotionality. The goal of the present study was to evaluate the independent and interactive effects of the stimulant response, assessed with an amphetamine challenge, and negative emotionality on alcohol and drug use. Methods Healthy young women and men completed the Multidimensional Personality Questionnaire (MPQ) and an inventory assessing alcohol and other drug use. Subsequently, the effects of 10 mg d-amphetamine were determined in the laboratory using the Stimulant scale of the Biphasic Alcohol Effects Scale. Hierarchical regression analyses evaluated the effects of amphetamine response and the MPQ factor Negative Emotionality on measures of substance use. Results The amphetamine response moderated relationships between negative emotionality and alcohol use: In combination with a robust amphetamine response (i.e., enhanced stimulant effects as compared to baseline), negative emotionality predicted greater alcohol consumption, more episodes of binge drinking, and more frequent intoxication in regression models. A strong stimulant response independently predicted having used an illicit drug, and there was a trend for it to predict having used alcohol. Negative emotionality alone was not associated with any measure of alcohol or drug use. Conclusions Consistent with the idea that emotion-based behavioral dysregulation promotes reward-seeking, a high level of negative emotionality was associated with maladaptive alcohol use when it co-occurred with sensitivity to drug-based reward. The findings contribute to our understanding of how differences in personality may interact with those in drug response to affect alcohol use. PMID:23240777

Selective mood-induced body image disparagement and enhancement effects: are they due to cognitive priming or subjective mood?

PubMed

Rotenberg, Ken J; Taylor, Daniel; Davis, Ron

2004-04-01

The study evaluated the effects of mood induction procedures on body image. Eighty female undergraduates participated in combinations of two valences (negative vs. positive) and two types (self-referent vs. other-referent) of mood induction procedures (MIPs). A measure of subjective mood and seven measures of body image were administered before and after the MIPs. Individuals in the self-referent MIP who had high negative body image at the pretest demonstrated increases in negative body image after exposure to the negative valence MIP (a disparagement effect) and decreases in negative body image after exposure to the positive valence MIP (an enhancement effect). This pattern was not evident in the other-referent MIP. Also, changes in negative body image were not appreciably associated with changes in subjective mood. The findings yielded support for the cognitive priming hypothesis but not for the subjective mood hypothesis. Further means of examining the cognitive priming hypothesis were outlined. Copyright 2004 by Wiley Periodicals, Inc. Int J Eat Disord 35: 317-332, 2004.

The moderating effects of aging and cognitive abilities on the association between work stress and negative affect.

PubMed

Hyun, Jinshil; Sliwinski, Martin J; Almeida, David M; Smyth, Joshua M; Scott, Stacey B

2018-05-01

Given that the association between work stress and negative affect can exacerbate negative health and workplace outcomes, it is important to identify the protective and risk factors that moderate this association. Socioemotional aging and cognitive abilities might influence how people utilize emotion regulation skills and engage in practical problem solving to manage their work stress. The aim of this study is to examine whether age and cognitive abilities independently and interactively moderate the association between work-related stress and negative affect. A diverse working adult sample (N = 139, age 25-65, 69% of females) completed a cross-sectional survey that assessed chronic work stress, negative affect, and fluid and crystallized cognitive abilities. Results from regression analyses suggested that both fluid and crystallized cognitive abilities, but not age, moderated the association between work stress and negative affect. Further, we found that crystallized cognition had a stronger attenuating effect on the work stress-negative affect association for older compared to younger workers. The moderating effect of fluid cognition was invariant across age. Our findings demonstrate that cognitive abilities are an important personal resource that might protect individuals against the negative impacts of work stress and negative affect. Although the role that fluid cognition plays in work stress-negative affect association is comparably important for both younger and older workers, crystallized cognition might play a more valuable role for older than younger workers.

Valence asymmetries in attitude ambivalence.

PubMed

Snyder, Aaron I; Tormala, Zakary L

2017-04-01

Existing models of ambivalence suggest that as the number of conflicting reactions (e.g., attitude components) increases, so too does the experience of ambivalence. Interestingly, though, these models overwhelmingly assume that this relationship is independent of valence. Across 3 studies we observe that this effect is in fact heavily influenced by 2 established valence asymmetries: positivity offset (baseline positive reactions even in the absence of positive information) and negativity bias (greater impact of negative reactions than positive reactions). Consistent with positivity offset, we observe that subjective ambivalence is greater when people have univalent negative rather than univalent positive attitudes. However, as conflicting information is acquired, subjective ambivalence rises more quickly when that information is negative rather than positive. The latter effect is consistent with negativity bias and suggests that although people feel more conflicted when they have only negative (vs. only positive) reactions, they also feel more conflicted when they have mostly positive (vs. mostly negative) reactions. Our investigation also uncovers an interesting consequence of these asymmetries: When people have mixed reactions, they do not experience maximum ambivalence at equal levels of positivity and negativity, as suggested by canonical ambivalence theory. Rather, subjective ambivalence peaks when positive reactions outnumber negative reactions. These effects are found to have downstream consequences for other dimensions of attitude strength. (PsycINFO Database Record (c) 2017 APA, all rights reserved).

Feeling Better About Self After Receiving Negative Feedback: When the Sense That Ability Can Be Improved Is Activated.

PubMed

Hu, Xinyi; Chen, Yinghe; Tian, Baowei

2016-01-01

Past studies suggest that managers and educators often consider negative feedback as a motivator for individuals to think about their shortcomings and improve their work, but delivering negative feedback does not always achieve desired results. The present study, based on incremental theory, employed an intervention method to activate the belief that a particular ability could be improved after negative feedback. Three experiments tested the intervention effect on negative self-relevant emotion. Study 1 indicated conveying suggestions for improving ability reduced negative self-relevant emotion after negative feedback. Study 2 tested whether activating the sense of possible improvement in the ability could reduce negative self-relevant emotion. Results indicated activating the belief that ability could be improved reduced negative self-relevant emotion after failure, but delivering emotion management information alone did not yield the same effect. Study 3 extended the results by affirming the effort participants made in doing the test, and found the affirmation reduced negative self-relevant emotion. Collectively, the findings indicated focusing on the belief that the ability could be improved in the future can reduce negative self-relevant emotion after negative feedback.

Neural evidence for description dependent reward processing in the framing effect.

PubMed

Yu, Rongjun; Zhang, Ping

2014-01-01

Human decision making can be influenced by emotionally valenced contexts, known as the framing effect. We used event-related brain potentials to investigate how framing influences the encoding of reward. We found that the feedback related negativity (FRN), which indexes the "worse than expected" negative prediction error in the anterior cingulate cortex (ACC), was more negative for the negative frame than for the positive frame in the win domain. Consistent with previous findings that the FRN is not sensitive to "better than expected" positive prediction error, the FRN did not differentiate the positive and negative frame in the loss domain. Our results provide neural evidence that the description invariance principle which states that reward representation and decision making are not influenced by how options are presented is violated in the framing effect.

Work-life balance culture, work-home interaction, and emotional exhaustion: a structural equation modeling approach.

PubMed

Nitzsche, Anika; Pfaff, Holger; Jung, Julia; Driller, Elke

2013-01-01

To examine the relationships among employees' emotional exhaustion, positive and negative work-home interaction, and perceived work-life balance culture in companies. Data for this study were collected through online surveys of employees from companies in the micro- and nanotechnology sectors (N = 509). A structural equation modeling analysis was performed. A company culture perceived by employees as supportive of their work-life balance was found to have both a direct negative effect on emotional exhaustion and an indirect negative effect meditated by negative work-home interaction. In addition, whereas negative work-home interaction associated positively with emotional exhaustion, positive work-home interaction had no significant effect. The direct and indirect relationship between work-life balance culture and emotional exhaustion has practical implications for health promotion in companies.

A Newtonian approach to extraordinarily strong negative refraction.

PubMed

Yoon, Hosang; Yeung, Kitty Y M; Umansky, Vladimir; Ham, Donhee

2012-08-02

Metamaterials with negative refractive indices can manipulate electromagnetic waves in unusual ways, and can be used to achieve, for example, sub-diffraction-limit focusing, the bending of light in the 'wrong' direction, and reversed Doppler and Cerenkov effects. These counterintuitive and technologically useful behaviours have spurred considerable efforts to synthesize a broad array of negative-index metamaterials with engineered electric, magnetic or optical properties. Here we demonstrate another route to negative refraction by exploiting the inertia of electrons in semiconductor two-dimensional electron gases, collectively accelerated by electromagnetic waves according to Newton's second law of motion, where this acceleration effect manifests as kinetic inductance. Using kinetic inductance to attain negative refraction was theoretically proposed for three-dimensional metallic nanoparticles and seen experimentally with surface plasmons on the surface of a three-dimensional metal. The two-dimensional electron gas that we use at cryogenic temperatures has a larger kinetic inductance than three-dimensional metals, leading to extraordinarily strong negative refraction at gigahertz frequencies, with an index as large as -700. This pronounced negative refractive index and the corresponding reduction in the effective wavelength opens a path to miniaturization in the science and technology of negative refraction.

Associations Between Infant Negative Affect and Parent Anxiety Symptoms are Bidirectional: Evidence from Mothers and Fathers

PubMed Central

Brooker, Rebecca J.; Neiderhiser, Jenae M.; Leve, Leslie D.; Shaw, Daniel S.; Scaramella, Laura V.; Reiss, David

2015-01-01

Little is known about child-based effects on parents’ anxiety symptoms early in life despite the possibility that child characteristics may contribute to the quality of the early environment and children’s own long-term risk for psychological disorder. We examined bidirectional effects between parent anxiety symptoms and infant negative affect using a prospective adoption design. Infant negative affect and adoptive parent anxiety symptoms were assessed at child ages 9, 18, and 27 months. Birth parent negative affect was assessed at child age 18 months. More anxiety symptoms in adoptive parents at child age 9 months predicted more negative affect in infants 9 months later. More infant negative affect at child age 9 months predicted more anxiety symptoms in adoptive parents 18 months later. Patterns of results did not differ for adoptive mothers and adoptive fathers. Birth parent negative affect was unrelated to infant or adoptive parent measures. Consistent with expectations, associations between infant negative affect and rearing parents’ anxiety symptoms appear to be bidirectional. In addition to traditional parent-to-child effects, our results suggest that infants’ characteristics may contribute to parent qualities that are known to impact childhood outcomes. PMID:26696939

Effect of post-encoding emotion on recollection and familiarity for pictures.

PubMed

Wang, Bo; Ren, Yanju

2017-07-01

Although prior studies have examined the effect of post-encoding emotional arousal on recognition memory for words, it is unknown whether the enhancement effect observed on words generalizes to pictures. Furthermore, prior studies using words have showed that the effect of emotional arousal can be modulated by stimuli valence and delay in emotion induction, but it is unclear whether such modulation can extend to pictures and whether other factors such as encoding method (incidental vs. intentional encoding) can be modulatory. Five experiments were conducted to answer these questions. In Experiment 1, participants encoded a list of neutral and negative pictures and then watched a 3-min neutral or negative video. The delayed test showed that negative arousal impaired recollection regardless of picture valence but had no effect on familiarity. Experiment 2 replicated the above findings. Experiment 3 was similar to Experiment 1 except that participants watched a 3-min neutral, negative, or positive video and conducted free recall before the recognition test. Unlike the prior two experiments, the impairment effect of negative arousal disappeared. Experiment 4, where the free recall task was eliminated, replicated the results from Experiment 3. Experiment 5 replicated Experiments 1 and 2 and further showed that the impairment effects of negative arousal could be modulated by delay in emotion induction but not by encoding method or stimuli valence. Taken together, the current study suggests that the enhancement effect observed on words may not generalize to pictures.

Generation and context memory.

PubMed

Mulligan, Neil W; Lozito, Jeffrey P; Rosner, Zachary A

2006-07-01

Generation enhances memory for occurrence but may not enhance other aspects of memory. The present study further delineates the negative generation effect in context memory reported in N. W. Mulligan (2004). First, the negative generation effect occurred for perceptual attributes of the target item (its color and font) but not for extratarget aspects of context (location and background color). Second, nonvisual generation tasks with either semantic or nonsemantic generation rules (antonym and rhyme generation, respectively) produced the same pattern of results. In contrast, a visual (or data-driven) generation task (letter transposition) did not disrupt context memory for color. Third, generating nonwords produced no effect on item memory but persisted in producing a negative effect on context memory for target attributes, implying that (a) the negative generation effect in context memory is not mediated by semantic encoding, and (b) the negative effect on context memory can be dissociated from the positive effect on item memory. The results are interpreted in terms of the processing account of generation. The original, perceptual-conceptual version of this account is too narrow, but a modified processing account, based on a more generic visual versus nonvisual processing distinction, accommodates the results. Copyright 2006 APA, all rights reserved.

Understanding the Function of Emotional Eating: Does it Buffer the Stress Response and Help Us Cope

DTIC Science & Technology

2008-05-09

Eating and Coping 25 these negative effects were most likely related to their presumed impact on health and weight. E. Comfort Foods...2003). Coping strategies can either amplify or reduce the stress experience, and therefore can either negatively or positively effect health...clinical behavior to understand. Finally, the effectiveness of stressors is much higher for negative stress than for positive (Westermann et al., 1996

Estimates of 2012/13 influenza vaccine effectiveness using the case test-negative control design with different influenza negative control groups.

PubMed

Nunes, Baltazar; Machado, Ausenda; Guiomar, Raquel; Pechirra, Pedro; Conde, Patrícia; Cristovão, Paula; Falcão, Isabel

2014-07-31

In recent years several reports of influenza vaccine effectiveness (VE) have been made early for public health decision. The majority of these studies use the case test-negative control design (TND), which has been showed to provide, under certain conditions, unbiased estimates of influenza VE. Nevertheless, discussions have been taken on the best influenza negative control group to use. The present study aims to contribute to the knowledge on this field by comparing influenza VE estimates using three test-negative controls: all influenza negative, non-influenza respiratory virus and pan-negative. Incident ILI patients were prospectively selected and swabbed by a sample of general practitioners. Cases were ILI patients tested positive for influenza and controls ILI patients tested negative for influenza. The influenza negative control group was divided into non-influenza virus control group and pan-negative control group. Data were collected on vaccination status and confounding factors. Influenza VE was estimated as one minus the odds ratio of been vaccinated in cases versus controls adjusted for confounding effect by logistic regression. Confounder adjusted influenza VE against medically attended laboratory-confirmed influenza was 68.4% (95% CI: 20.7-87.4%) using all influenza negatives controls, 82.1% (95% CI: 47.6-93.9%) using non-influenza controls and 49.4% (95% CI: -44.7% to 82.3%) using pan-negative controls. Influenza VE estimates differed according to the influenza negative control group used. These results are in accordance with the expected under the hypothesis of differential viral interference between influenza vaccinated and unvaccinated individuals. Given the wide importance of TND study further studies should be conducted in order to clarify the observed differences. Copyright © 2014 Elsevier Ltd. All rights reserved.

Heat shock protein 90 (HSP90) is overexpressed in p16-negative oropharyngeal squamous cell carcinoma, and its inhibition in vitro potentiates the effects of chemoradiation.

PubMed

Patel, Kirtesh; Wen, Jing; Magliocca, Kelly; Muller, Susan; Liu, Yuan; Chen, Zhuo Georgia; Saba, Nabil; Diaz, Roberto

2014-11-01

Cisplatin and radiation therapy remain the current standard for treating locally advanced SCCHN. Novel treatment approaches are needed, especially in patients with human papilloma virus (HPV)-negative disease who have worse outcomes despite multimodality therapy. Using our institutional review board approved database, we obtained twenty oropharyngeal squamous cell carcinoma (SCC) tissue samples: ten p16 positive, ten p16-negative. Because p16 expression is strongly associated with HPV positivity in oropharyngeal SCC, p16 status was used as a marker of HPV. We subsequently analyzed, via immunohistochemistry, heat shock protein 90 (HSP90) protein levels. Using HPV-positive and HPV-negative SCC cell lines, we compared baseline HSP90 expression levels and the effect of the HSP90 inhibitor ganetespib on viability and apoptosis. Clonogenic survival of HPV-negative cells treated with ganetespib, radiation therapy, and/or cisplatin was then investigated. We characterize the effects of ganetespib on proteins that are thought to drive DNA damage resistance in HPV-negative cells. HSP90 expression was significantly higher in p16-negative compared with p16-positive samples (p = 0.016) and in HPV-negative cell lines compared with positive cells. Ganetespib increased cytotoxicity and induced apoptosis in HPV-negative more than positive cells. Adding ganetespib to cisplatin and/or radiation therapy in HPV-negative cells further decreased clonogenic survival. Finally, ganetespib downregulated expressions of EGFR, ERK, AKT, p53, and HIF-1α. Ganetespib inhibited HPV-negative SCCHN viability and potentiated cell kill when combined with cisplatin or radiation therapy in vitro. With HSP90 expression higher in HPV-negative cells and in p16-negative patients, further exploration of the clinical activity of HSP90 inhibitors in SCCHN is warranted.

Inverse Doppler Effects in Broadband Acoustic Metamaterials

PubMed Central

Zhai, S. L.; Zhao, X. P.; Liu, S.; Shen, F. L.; Li, L. L.; Luo, C. R.

2016-01-01

The Doppler effect refers to the change in frequency of a wave source as a consequence of the relative motion between the source and an observer. Veselago theoretically predicted that materials with negative refractions can induce inverse Doppler effects. With the development of metamaterials, inverse Doppler effects have been extensively investigated. However, the ideal material parameters prescribed by these metamaterial design approaches are complex and also challenging to obtain experimentally. Here, we demonstrated a method of designing and experimentally characterising arbitrary broadband acoustic metamaterials. These omni-directional, double-negative, acoustic metamaterials are constructed with ‘flute-like’ acoustic meta-cluster sets with seven double meta-molecules; these metamaterials also overcome the limitations of broadband negative bulk modulus and mass density to provide a region of negative refraction and inverse Doppler effects. It was also shown that inverse Doppler effects can be detected in a flute, which has been popular for thousands of years in Asia and Europe. PMID:27578317

Inverse Doppler Effects in Broadband Acoustic Metamaterials

NASA Astrophysics Data System (ADS)

Zhai, S. L.; Zhao, X. P.; Liu, S.; Shen, F. L.; Li, L. L.; Luo, C. R.

2016-08-01

The Doppler effect refers to the change in frequency of a wave source as a consequence of the relative motion between the source and an observer. Veselago theoretically predicted that materials with negative refractions can induce inverse Doppler effects. With the development of metamaterials, inverse Doppler effects have been extensively investigated. However, the ideal material parameters prescribed by these metamaterial design approaches are complex and also challenging to obtain experimentally. Here, we demonstrated a method of designing and experimentally characterising arbitrary broadband acoustic metamaterials. These omni-directional, double-negative, acoustic metamaterials are constructed with ‘flute-like’ acoustic meta-cluster sets with seven double meta-molecules; these metamaterials also overcome the limitations of broadband negative bulk modulus and mass density to provide a region of negative refraction and inverse Doppler effects. It was also shown that inverse Doppler effects can be detected in a flute, which has been popular for thousands of years in Asia and Europe.

What matters when judging intentionality-moral content or normative status? Testing the rational scientist model of the side-effect.

PubMed

Papadopoulos, C; Hayes, B K

2018-06-01

Previous work has demonstrated a "side-effect effect," such that intentionality is more likely to be attributed to agents who bring about negatively valenced as opposed to positively valenced side effects. The rational-scientist model explains this by suggesting that norm-violating side effects are more informative for inferring intentionality than norm-conforming side effects. In the present study we reexamined this account, addressing limitations of previous empirical tests (e.g., Uttich & Lombrozo, Cognition 116: 87-100, 2010). Side-effect valence and norm status were manipulated factorially, enabling an examination of the impact of norm status on intentionality judgments in both positively and negatively valenced side effects. Additionally, the impact of side-effect norm status on the perceived valences of side effects and agents was examined. Effects of norm status were found for both positive and negative side effects. Violation of an ostensibly neutral norm led to negative perceptions of the side effect. However, a norm status effect on intentionality judgments persisted when these effects were controlled. These results support the view that the side-effect effect is the result of the rational use of social-cognitive evidence.

Learning to Dislike Chocolate: Conditioning Negative Attitudes toward Chocolate and Its Effect on Chocolate Consumption.

PubMed

Wang, Yan; Wang, Guosen; Zhang, Dingyuan; Wang, Lei; Cui, Xianghua; Zhu, Jinglei; Fang, Yuan

2017-01-01

Evaluative conditioning (EC) procedures can be used to form and change attitudes toward a wide variety of objects. The current study examined the effects of a negative EC procedure on attitudes toward chocolate, and whether it influenced chocolate evaluation and consumption. Participants were randomly assigned to the experimental condition in which chocolate images were paired with negative stimuli, or the control condition in which chocolate images were randomly paired with positive stimuli (50%) and negative stimuli (50%). Explicit and implicit attitudes toward chocolate images were collected. During an ostensible taste test, chocolate evaluation and consumption were assessed. Results revealed that compared to participants in the control condition, participants in the experimental condition showed more negative explicit and implicit attitudes toward chocolate images and evaluated chocolate more negatively during the taste test. However, chocolate consumption did not differ between experimental and control conditions. These findings suggest that pairing chocolate with negative stimuli can influence attitudes toward chocolate, though behavioral effects are absent. Intervention applications of EC provide avenues for future research and practices.

Are positive and negative reinforcement "different"? Insights from a free-operant differential outcomes effect.

PubMed

Magoon, Michael A; Critchfield, Thomas S; Merrill, Dustin; Newland, M Christopher; Schneider, W Joel

2017-01-01

Although theoretical discussions typically assume that positive and negative reinforcement differ, the literature contains little unambiguous evidence that they produce differential behavioral effects. To test whether the two types of consequences control behavior differently, we pitted money-gain positive reinforcement and money-loss-avoidance negative reinforcement, scheduled through identically programmed variable-cycle schedules, against each other in concurrent schedules. Contingencies of response-produced feedback, normally different in positive and negative reinforcement, were made symmetrical. Steeper matching slopes were produced compared to a baseline consisting of all positive reinforcement. This free-operant differential outcomes effect supports the notion that that stimulus-presentation positive reinforcement and stimulus-elimination negative reinforcement are functionally "different." However, a control experiment showed that the feedback asymmetry of more traditional positive and negative reinforcement schedules also is sufficient to create a "difference" when the type of consequence is held constant. We offer these findings as a small step in meeting the very large challenge of moving negative reinforcement theory beyond decades of relative quiescence. © 2017 Society for the Experimental Analysis of Behavior.

Learning to Dislike Chocolate: Conditioning Negative Attitudes toward Chocolate and Its Effect on Chocolate Consumption

PubMed Central

Wang, Yan; Wang, Guosen; Zhang, Dingyuan; Wang, Lei; Cui, Xianghua; Zhu, Jinglei; Fang, Yuan

2017-01-01

Evaluative conditioning (EC) procedures can be used to form and change attitudes toward a wide variety of objects. The current study examined the effects of a negative EC procedure on attitudes toward chocolate, and whether it influenced chocolate evaluation and consumption. Participants were randomly assigned to the experimental condition in which chocolate images were paired with negative stimuli, or the control condition in which chocolate images were randomly paired with positive stimuli (50%) and negative stimuli (50%). Explicit and implicit attitudes toward chocolate images were collected. During an ostensible taste test, chocolate evaluation and consumption were assessed. Results revealed that compared to participants in the control condition, participants in the experimental condition showed more negative explicit and implicit attitudes toward chocolate images and evaluated chocolate more negatively during the taste test. However, chocolate consumption did not differ between experimental and control conditions. These findings suggest that pairing chocolate with negative stimuli can influence attitudes toward chocolate, though behavioral effects are absent. Intervention applications of EC provide avenues for future research and practices. PMID:28900409

Promoting walking in older adults: Perceived neighborhood walkability influences the effectiveness of motivational messages

PubMed Central

Notthoff, Nanna; Carstensen, Laura L.

2015-01-01

Positively-framed messages seem to promote walking in older adults better than negatively-framed messages. This study targeted elderly people in communities unfavorable to walking. Walking was measured with pedometers during baseline (one week) and intervention (four weeks). Participants (n = 74) were either informed about the benefits of walking or the negative consequences of not walking. Perceived neighborhood walkability was assessed with a modified version of the Neighborhood Walkability Scale. When perceived walkability was high positively-framed messages were more effective than negatively-framed messages in promoting walking; when perceived walkability was low negatively-framed messages were comparably effective to positively-framed messages. PMID:26604128

Conflict-driven adaptive control is enhanced by integral negative emotion on a short time scale.

PubMed

Yang, Qian; Pourtois, Gilles

2018-02-05

Negative emotion influences cognitive control, and more specifically conflict adaptation. However, discrepant results have often been reported in the literature. In this study, we broke down negative emotion into integral and incidental components using a modern motivation-based framework, and assessed whether the former could change conflict adaptation. In the first experiment, we manipulated the duration of the inter-trial-interval (ITI) to assess the actual time-scale of this effect. Integral negative emotion was induced by using loss-related feedback contingent on task performance, and measured at the subjective and physiological levels. Results showed that conflict-driven adaptive control was enhanced when integral negative emotion was elicited, compared to a control condition without changes in defensive motivation. Importantly, this effect was only found when a short, as opposed to long ITI was used, suggesting that it had a short time scale. In the second experiment, we controlled for effects of feature repetition and contingency learning, and replicated an enhanced conflict adaptation effect when integral negative emotion was elicited and a short ITI was used. We interpret these new results against a standard cognitive control framework assuming that integral negative emotion amplifies specific control signals transiently, and in turn enhances conflict adaptation.

Neuroticism, coping strategies, and negative well-being among caregivers.

PubMed

Patrick, J H; Hayden, J M

1999-06-01

Neuroticism was incorporated into a model for predicting the well-being of family caregivers. Using data from 596 women with an adult child with a chronic disability, the model hypothesizes direct effects of neuroticism on a caregiver's perceptions of the stressor, on her wishful-escapism and problem-focused coping, and on psychological well-being. Results indicate that neuroticism exerts direct and indirect effects on negative well-being. Results also indicate that stressors have direct effects on both wishful-escapism coping and problem-focused coping. Burden had direct effects on negative psychological well-being. Diagnosis influences the model by having direct effects on stressors and wishful-escapism coping but not on problem-focused coping or burden. Inclusion of individual level variables, such as neuroticism, results in a substantial amount of explained variance in negative well-being.

Benefits of negative social exchanges for emotional closeness.

PubMed

Fung, Helene H; Yeung, Dannii Y; Li, Kin-Kit; Lang, Frieder R

2009-09-01

Negative exchanges in social relationships have traditionally been studied as having negative consequences. This study explored whether they might have positive effects for relationship closeness. The sample included 351 adults, aged between 18 and 91 years, residing in Hong Kong, China. Closeness of social partners to the participants was measured by the Social Convoy Questionnaire, and the levels of negative exchanges and social support from each social partner were assessed. Multilevel analyses revealed that more negative exchanges were associated with a more positive change in closeness over a 2-year period, even after statistically controlling for social support and sociostructural characteristics of the participant and the social partner. Findings extended our knowledge on the positive effects of negative exchanges and their moderating conditions.

Negative index effects from a homogeneous positive index prism

NASA Astrophysics Data System (ADS)

Marcus, Sherman W.; Epstein, Ariel

2017-12-01

Cellular structured negative index metamaterials in the form of a right triangular prism have often been tested by observing the refraction of a beam across the prism hypotenuse which is serrated in order to conform to the cell walls. We show that not only can this negative index effect be obtained from a homogeneous dielectric prism having a positive index of refraction, but in addition, for sampling at the walls of the cellular structure, the phase in the material has the illusory appearance of moving in a negative direction. Although many previous reports relied on refraction direction and phase velocity of prism structures to verify negative index design, our investigation indicates that to unambiguously demonstrate material negativity additional empirical evidence is required.

Can Contrast Effects Regulate Emotions? A Follow-Up Study of Vital Loss Decisions

PubMed Central

Liu, Xianyun; Luo, Jing

2012-01-01

Although many studies focus on the how contrast effects can impact cognitive evaluations, the question of whether emotions are regulated by such contrast effects is still the subject of considerable debate, especially in the study of loss-related decisions. To address this gap in the literature, we designed three decision making loss conditions: (i) both losses are trivial (TT), (ii) one loss is trivial and the other loss is vital (TV), or (iii) one loss is trivial and the other loss is routine (TR). In study 1, which compared the difference between the negative emotion ratings in TT and TV, we found that negative emotions were affected by the contrast effects. In study 2, which compared the difference between the importance of trivial options in TT and TV, we found that the contrast effects differentially changed the importance of trivial options in the two conditions, which in turn down-regulated negative emotions. In study 3, the impact of decision difficulty was controlled by predetermining the items to be lost. In this study, we found that, when comparing the differences between the negative emotions of losing trivial options in TV and TR, the contrast effects still modulated the loss-related emotions. We concluded that the contrast effects could down-regulate emotions. To our knowledge, this is the first demonstration that contrast effects can alleviate negative affect in loss-related decision making. This study will enrich and extend the literature on emotion regulation theory, and it will provide a new cost-effective mitigation strategy for regulating negative emotions. PMID:22905170

Targeted Gene Silencing of Tumor Necrosis Factor Attenuates the Negative Inotropic Effects of Lipopolysaccharide in Isolated Contracting Cardiac Myocytes

PubMed Central

Ramabadran, R. S.; Chancey, Amanda; Vallejo, Jesus G.; Barger, Philip M.; Sivasubramanian, Natarajan; Mann, Douglas L.

2008-01-01

Bacterial endotoxin (lipopolysaccharide) depresses cardiovascular function; however, the mediators and signaling pathways that are responsible for the negative inotropic effects of lipopolysaccharide are not fully known. We used RNA interference to determine the relative role of tumor necrosis factor with respect to mediating the negative inotropic effects of lipopolysaccharide in isolated cardiac myocytes. Cardiac myocyte cultures were treated with lipopolysaccharide in the presence or absence of small interfering RNAs (siRNA) for tumor necrosis factor. We examined the effects of tumor necrosis factor siRNA on lipopolysaccharide-induced tumor necrosis factor messenger RNA (mRNA) and protein biosynthesis, as well as the negative inotropic effects of lipopolysaccharide in isolated contracting cardiac myocytes. Treatment of adult cardiac myocyte cultures with tumor necrosis factor siRNA significantly attenuated lipopolysaccharide-induced tumor necrosis factor mRNA and protein biosynthesis, whereas transfection with a double-stranded RNA that does not target mammalian mRNA had no effect. Pretreatment with tumor necrosis factor siRNA significantly attenuated, but did not abrogate, the lipopolysaccharide-induced decrease in sarcomere shortening in isolated contracting cardiac myocytes. In contrast, tumor necrosis factor siRNA had a comparatively smaller effect on improving sarcomere shortening once the negative inotropic effects of lipopolysaccharide were fully established. These results suggest that tumor necrosis factor plays an important upstream role in lipopolysaccharide-induced negative inotropic effects in isolated contracting cardiac myocytes and that other molecular mechanisms are responsible for the decrease in sarcomere shortening after sustained lipopolysaccharide signaling. PMID:18427645

Glyceollins as novel targeted therapeutic for the treatment of metastatic triple-negative breast cancer

USDA-ARS?s Scientific Manuscript database

The purpose of this study was to investigate the effects of glyceollins on the suppression of tumorigenesis in triple negative breast carcinoma cell lines. We further explored the effects of glyceollins on microRNA and protein expression in MDA MB 231 cells. Triple negative (ER , PgR, and Her2/neu ...

Nickel cadmium cell designs negative to positive material ratio and precharge levels

NASA Technical Reports Server (NTRS)

Gross, S.

1977-01-01

A review is made of the factors affecting the choices of negative-to-positive materials ratio and negative precharge in nickel-cadmium cells. The effects of these variables on performance are given, and the different methods for setting precharge are evaluated. The effects of special operating requirements on the design are also discussed.

A Fine-Grained Analysis of the Effects of Negative Evidence with and without Metalinguistic Information in Language Development

ERIC Educational Resources Information Center

Lado, Beatriz; Bowden, Harriet Wood; Stafford, Catherine A; Sanz, Cristina

2014-01-01

The current study compared the effectiveness of computer-delivered task-essential practice coupled with feedback consisting of (1) negative evidence with metalinguistic information (NE+MI) or (2) negative evidence without metalinguistic information (NE-MI) in promoting absolute beginners' (n = 58) initial learning of aspects of Latin…

On Buffers and Boosters: Social Support for Negative and Positive Life Events.

ERIC Educational Resources Information Center

Sandler, Irwin N.

Social support has been studied in the context of its relationship to and effect on negative experiences. While this buffer aspect of social support is important, support may also play a satisfaction-enhancing role. Both the negative event-buffering and positive event-boosting effect of social support on students' satisfaction with their college…

Negative Affect and Alcohol Use among Non-Hispanic White and Mexican American Adolescents.

ERIC Educational Resources Information Center

Swaim, Randall C.; Chen, Julie; Deffenbacher, Jerry L.; Newcomb, Michael D.

2001-01-01

Examines the effects of negative affect on adolescent alcohol use among non-Hispanic White and Mexican American 9-12th grade students. Results indicate that unique components of negative affect relate to adolescent alcohol use in different patterns across different groups of youth. However, the small magnitude of these effects calls into question…

Negative Effects of Reward on Intrinsic Motivation--A Limited Phenomenon: Comment on Deci, Koestner, and Ryan (2001).

ERIC Educational Resources Information Center

Cameron, Judy

2001-01-01

Prior meta analyses by J. Cameron and other researchers suggested that the negative effects of extrinsic reward on intrinsic motivation were limited and avoidable. E. Deci and others (2001) suggested that the analyses were flawed. This commentary makes the case that there is no inherent negative property of reward. (SLD)

Sex differences in effective fronto-limbic connectivity during negative emotion processing.

PubMed

Lungu, Ovidiu; Potvin, Stéphane; Tikàsz, Andràs; Mendrek, Adrianna

2015-12-01

In view of the greater prevalence of depression and anxiety disorders in women than in men, functional magnetic resonance imaging (fMRI) studies have examined sex-differences in brain activations during emotion processing. Comparatively, sex-differences in brain connectivity received little attention, despite evidence for important fronto-limbic connections during emotion processing across sexes. Here, we investigated sex-differences in fronto-limbic connectivity during negative emotion processing. Forty-six healthy individuals (25 women, 21 men) viewed negative, positive and neutral images during an fMRI session. Effective connectivity between significantly activated regions was examined using Granger causality and psychophysical interaction analyses. Sex steroid hormones and feminine-masculine traits were also measured. Subjective ratings of negative emotional images were higher in women than in men. Across sexes, significant activations were observed in the dorso-medial prefrontal cortex (dmPFC) and the right amygdala. Granger connectivity from right amygdala was significantly greater than that from dmPFC during the 'high negative' condition, an effect driven by men. Magnitude of this effect correlated negatively with highly negative image ratings and feminine traits and positively with testosterone levels. These results highlight critical sex differences in brain connectivity during negative emotion processing and point to the fact that both biological (sex steroid hormones) and psychosocial (gender role and identity) variables contribute to them. As the dmPFC is involved in social cognition and action planning, and the amygdala-in threat detection, the connectivity results suggest that compared to women, men have a more evaluative, rather than purely affective, brain response during negative emotion processing. Copyright © 2015 Elsevier Ltd. All rights reserved.

The interactive effects of negative symptoms and social role functioning on suicide ideation in individuals with schizophrenia.

PubMed

Jahn, Danielle R; Bennett, Melanie E; Park, Stephanie G; Gur, Raquel E; Horan, William P; Kring, Ann M; Blanchard, Jack J

2016-02-01

Findings regarding the protective effect of social role functioning on suicide ideation in individuals with schizophrenia have been mixed. One reason for such inconsistencies in the literature may be that individuals with prominent negative symptoms of schizophrenia may not experience a desire for social closeness, and therefore social role functioning may not influence suicide risk in these individuals. The aim of this study was to examine the moderating effects of self-reported desire for social closeness and interviewer-rated negative symptoms on the relationship between social role functioning and suicide ideation. Our sample consisted of 162 individuals who had been diagnosed with schizophrenia-spectrum disorders; all participants completed self-report questionnaires and clinician-administered interviews, and moderation hypotheses were tested with a non-parametric procedure. The results indicated that motivation and pleasure-related negative symptoms moderated the relationship between social role functioning and suicide ideation; self-reported desire for social closeness and negative symptoms related to expression did not have such a moderating effect. Specifically, better social role functioning was associated with less suicide ideation only in those individuals who had low motivation and pleasure-related negative symptoms; no significant relationship was observed between social role functioning and suicide ideation among those with elevated motivation and pleasure-related negative symptoms. These findings suggest that assessing for negative symptoms and social role functioning may inform suicide risk assessments in individuals with schizophrenia, and improving social role functioning may reduce suicide ideation among those with few motivation and pleasure-related negative symptoms. Copyright © 2015 Elsevier B.V. All rights reserved.

The roles of negative affect and goal adjustment capacities in breast cancer survivors: Associations with physical activity and diurnal cortisol secretion.

PubMed

Castonguay, Andree L; Wrosch, Carsten; Sabiston, Catherine M

2017-04-01

This study examined whether within-person changes of breast cancer survivors' high-arousal negative affect (e.g., feeling scared, upset, anxious, or guilty) could predict high levels of diurnal cortisol secretion and moderate-to-vigorous physical activity (MVPA). In addition, goal adjustment capacities (goal disengagement and goal reengagement) were expected to buffer the effect of negative affect on cortisol and to increase its effect on MVPA. High-arousal negative affect, self-reported MVPA, area-under-the-curve of diurnal cortisol secretion, and goal adjustment capacities were assessed in a longitudinal sample of 145 female breast cancer survivors. Based on hierarchical linear modeling, breast cancer survivors reported increased levels of both MVPA and cortisol secretion if they experienced higher (as compared with lower) levels of high-arousal negative affect than their personal average. Furthermore, within-person negative affect was associated with: (a) higher MVPA among participants with high (but not low) goal reengagement capacities; and (b) elevated cortisol secretion among participants with low (but not high) goal reengagement capacities. High-arousal negative affect may exert differing functions among breast cancer survivors in that it can trigger adaptive health behaviors, yet simultaneously elevate diurnal cortisol secretion. In addition, being able to engage in new goals may be a necessary condition for breast cancer survivors to experience the beneficial behavioral effects of high-arousal negative affect, and it may prevent the adverse effect of negative affect on enhanced cortisol output. (PsycINFO Database Record (c) 2017 APA, all rights reserved).

Effects of Sequential Fluoxetine and Gender on Pre-quit Depressive Symptoms, Affect, Craving, and Quit Day Abstinence in Smokers with Elevated Depressive Symptoms: A Growth Curve Modeling Approach

PubMed Central

Minami, Haruka; Kahler, Christopher W.; Bloom, Erika Litvin; Prince, Mark A.; Abrantes, Ana M.; Strong, David R.; Niaura, Raymond; Miller, Ivan W.; Palm Reed, Kathleen M.; Price, Lawrence H.; Brown, Richard A.

2015-01-01

While the important roles of post-quit affect and withdrawal symptoms in the process of smoking cessation have been well established, little is known about the relations between pre-quit affective trajectories and cessation outcome on the target quit date (TQD). This study examined whether a 16-week course of fluoxetine initiated 8 weeks pre-quit (“sequential” fluoxetine) improved TQD abstinence relative to placebo through its effects on pre-quit depressive symptoms, affect (withdrawal-relevant negative affect, general negative affect, and positive affect), and craving to smoke among 206 smokers with elevated depressed symptoms. The moderating effects of gender were also examined. A total of 83 smokers (40%) failed to achieve abstinence on TQD, with no difference between treatment conditions or gender. Overall structural equation models showed that fluoxetine had significant indirect effects on TQD abstinence through changes in pre-quit withdrawal-relevant negative affect and craving, but not depressive symptoms. However, multigroup analyses revealed gender differences. Sequential fluoxetine reduced pre-quit depressive symptoms, withdrawal-relevant negative affect, and craving only among women. Reduction in pre-quit depressive symptoms and craving among women, and withdrawal-relevant negative affect among men was associated with TQD abstinence. Moreover, exploratory analysis showed negative trend-level indirect effects of fluoxetine on TQD abstinence via increased side effects, regardless of gender. This study demonstrated the importance of considering gender when examining treatment efficacy. Identifying ways to further reduce pre-quit depressive symptoms and craving for women and withdrawal-relevant negative affect for men while alleviating side effects may help smokers with elevated depressed symptoms achieve the first smoking cessation milestone. PMID:25089930

Effects of Age on Negative Subsequent Memory Effects Associated with the Encoding of Item and Item–Context Information

PubMed Central

Mattson, Julia T.; Wang, Tracy H.; de Chastelaine, Marianne; Rugg, Michael D.

2014-01-01

It has consistently been reported that “negative” subsequent memory effects—lower study activity for later remembered than later forgotten items—are attenuated in older individuals. The present functional magnetic resonance imaging study investigated whether these findings extend to subsequent memory effects associated with successful encoding of item–context information. Older (n = 25) and young (n = 17) subjects were scanned while making 1 of 2 encoding judgments on a series of pictures. Memory was assessed for the study item and, for items judged old, the item's encoding task. Both memory judgments were made using confidence ratings, permitting item and source memory strength to be unconfounded and source confidence to be equated across age groups. Replicating prior findings, negative item effects in regions of the default mode network in young subjects were reversed in older subjects. Negative source effects, however, were invariant with respect to age and, in both age groups, the magnitude of the effects correlated with source memory performance. It is concluded that negative item effects do not reflect processes necessary for the successful encoding of item–context associations in older subjects. Negative source effects, in contrast, appear to reflect the engagement of processes that are equally important for successful episodic encoding in older and younger individuals. PMID:23904464

Effects of Soldiers’ Deployment on Children’s Academic Performance and Behavioral Health

DTIC Science & Technology

2011-01-01

tests. We found a negative relationship between the cumulative months a parent had deployed and achievement test scores across states (North Carolina...strongest negative relationship with cumulative parental deployment of 1 to 18 months and 19 months or more, and this effect size is larger than...that the negative effect of parental deployment on academic scores is more pronounced on elementary-age children (grades 3–6) than on secondary-age

Meta-analysis of the effects of repetitive transcranial magnetic stimulation (rTMS) on negative and positive symptoms in schizophrenia

PubMed Central

Freitas, Catarina; Fregni, Felipe; Pascual-Leone, Alvaro

2009-01-01

Background A growing body of evidence suggests that repetitive transcranial magnetic stimulation (rTMS) can alleviate negative and positive symptoms of refractory schizophrenia. However, trials to date have been small and results are mixed. Methods We performed meta-analyses of all prospective studies of the therapeutic application of rTMS in refractory schizophrenia assessing the effects of high-frequency rTMS to the left dorsolateral prefrontal cortex (DLPFC) to treat negative symptoms, and low-frequency rTMS to the left temporo-parietal cortex (TPC) to treat auditory hallucinations (AH) and overall positive symptoms. Results When analyzing controlled (active arms) and uncontrolled studies together, the effect sizes showed significant and moderate effects of rTMS on negative and positive symptoms (based on PANSS-N or SANS, and PANSS-P or SAPS, respectively). However, the analysis for the sham-controlled studies revealed a small non-significant effect size for negative (0.27, p=0.417) and for positive symptoms (0.17, p=0.129). When specifically analyzing AH (based on AHRS, HCS or SAH), the effect size for the sham-controlled studies was large and significant (1.04; p=0.002). Conclusions These meta-analyses support the need for further controlled, larger trials to assess the clinical efficacy of rTMS on negative and positive symptoms of schizophrenia, while suggesting the need for exploration for alternative stimulation protocols. PMID:19138833

Negative ions of polyatomic molecules.

PubMed Central

Christophorou, L G

1980-01-01

In this paper general concepts relating to, and recent advances in, the study of negative ions of polyatomic molecules area discussed with emphasis on halocarbons. The topics dealt with in the paper are as follows: basic electron attachment processes, modes of electron capture by molecules, short-lived transient negative ions, dissociative electron attachment to ground-state molecules and to "hot" molecules (effects of temperature on electron attachment), parent negative ions, effect of density, nature, and state of the medium on electron attachment, electron attachment to electronically excited molecules, the binding of attached electrons to molecules ("electron affinity"), and the basic and the applied significance of negative-ion studies. PMID:7428744

Negative emotion elicited in high school students enhances consolidation of item memory, but not source memory.

PubMed

Wang, Bo

2015-05-01

The study examined the effect of negative emotion on consolidation of both item and source memory. Participants learned words read by either a male or female. Then they watched either a negative or a neutral video clip. Memory tests were carried out either 25min or 24h after learning. The study yielded the following findings. First, negative emotion enhanced consolidation of item memory as measured by recognition memory in the 25-min delay, and enhanced consolidation of item memory as measured by free recall in both the 25-min and the 24-h delay. Second, negative emotion had little effect on consolidation of source memory, either in the 25-min or the 24-h delay. These findings provide evidence for the differential effects of negative emotion on item memory and source memory and have implications for using emotion as a strategy to intervene memory consolidation. Copyright © 2015 Elsevier Inc. All rights reserved.

'Help me! I'm old!' How negative aging stereotypes create dependency among older adults.

PubMed

Coudin, Genevieve; Alexopoulos, Theodore

2010-07-01

This study examined the effects of negative aging stereotypes on self-reported loneliness, risk-taking, subjective health, and help-seeking behavior in a French sample of older adults. The aim of this study was to show the detrimental effects of negative aging stereotypes on older adults' self-evaluations and behaviors, therefore contributing to the explanations of the iatrogenic effect of social environments that increase dependency (e.g., health care institutions). In the first experiment conducted on 57 older adults, we explored the effects of positive, neutral, or negative stereotype activation on the feeling of loneliness and risk taking decision. The second experiment (n = 60) examined the impact of stereotype activation on subjective health, self-reported extraversion as well as on a genuine help-seeking behavior, by allowing participants to ask for the experimenter's help while completing a task. As predicted, negative stereotype activation resulted in lower levels of risk taking, subjective health and extraversion, and in higher feelings of loneliness and a more frequent help-seeking behavior. These findings suggest that the mere activation of negative stereotypes can have broad and deleterious effects on older individuals' self-evaluation and functioning, which in turn may contribute to the often observed dependency among older people.

Neural evidence for description dependent reward processing in the framing effect

PubMed Central

Yu, Rongjun; Zhang, Ping

2014-01-01

Human decision making can be influenced by emotionally valenced contexts, known as the framing effect. We used event-related brain potentials to investigate how framing influences the encoding of reward. We found that the feedback related negativity (FRN), which indexes the “worse than expected” negative prediction error in the anterior cingulate cortex (ACC), was more negative for the negative frame than for the positive frame in the win domain. Consistent with previous findings that the FRN is not sensitive to “better than expected” positive prediction error, the FRN did not differentiate the positive and negative frame in the loss domain. Our results provide neural evidence that the description invariance principle which states that reward representation and decision making are not influenced by how options are presented is violated in the framing effect. PMID:24733998

Novel stimuli are negative stimuli: evidence that negative affect is reduced in the mere exposure effect.

PubMed

Robinson, Brent M; Elias, Lorin J

2005-04-01

Repeated exposure of a nonreinforced stimulus results in an increased preference for that stimulus, the mere exposure effect. The present study repeatedly presented positive, negative, and neutrally affective faces to 48 participants while they made judgments about the emotional expression. Participants then rated the likeability of novel neutrally expressive faces and some of these previously presented faces, this time in their neutral expression. Faces originally presented as happy were rated as the most likeable, followed by faces originally presented as neutral. Negative and novel faces were not rated significantly differently from each other. These findings support the notion that the increase in preference towards repeatedly presented stimuli is the result of the reduction in negative affect, consistent with the modified two-factor uncertainty-reduction model and classical conditioning model of the mere exposure effect.

Similarity to the Self Affects Memory for Impressions of Others in Younger and Older Adults

PubMed Central

Park, Jung M.; Gutchess, Angela H.

2015-01-01

Objectives. Similarity to the self has been shown to affect memory for impressions in younger adults, suggesting a self-reference effect in person memory. Because older adults show comparable self-reference effects, but prioritize memory for positive over negative information relative to young adults, we examined age differences in self-similarity effects on memory for positive and negative impressions. Method. Younger and older adults formed positive and negative impressions of others differing in the degree of similarity to the self (high, medium, low). Results. For positive impressions, both groups showed enhanced memory for self-similar others relative to dissimilar others, whereas for negative impressions, memory was poorer for those similar to the self. When collapsed across similarity to the self, younger adults remembered negative impressions better than older adults, but interestingly, older adults exhibited a trend for better memory for the positive impressions. Discussion. Results suggest that self-reference effects in impression memory are preserved with age and that older adults exhibit positivity effects in person memory consistent with previous findings. PMID:24389124

Positive messaging promotes walking in older adults.

PubMed

Notthoff, Nanna; Carstensen, Laura L

2014-06-01

Walking is among the most cost-effective and accessible means of exercise. Mounting evidence suggests that walking may help to maintain physical and cognitive independence in old age by preventing a variety of health problems. However, older Americans fall far short of meeting the daily recommendations for walking. In 2 studies, we examined whether considering older adults' preferential attention to positive information may effectively enhance interventions aimed at promoting walking. In Study 1, we compared the effectiveness of positive, negative, and neutral messages to encourage walking (as measured with pedometers). Older adults who were informed about the benefits of walking walked more than those who were informed about the negative consequences of failing to walk, whereas younger adults were unaffected by framing valence. In Study 2, we examined within-person change in walking in older adults in response to positively- or negatively-framed messages over a 28-day period. Once again, positively-framed messages more effectively promoted walking than negatively-framed messages, and the effect was sustained across the intervention period. Together, these studies suggest that consideration of age-related changes in preferences for positive and negative information may inform the design of effective interventions to promote healthy lifestyles. Future research is needed to examine the mechanisms underlying the greater effectiveness of positively- as opposed to negatively-framed messages and the generalizability of findings to other intervention targets and other subpopulations of older adults. PsycINFO Database Record (c) 2014 APA, all rights reserved.

Sphingosine mediates the immediate negative inotropic effects of tumor necrosis factor-alpha in the adult mammalian cardiac myocyte.

PubMed

Oral, H; Dorn, G W; Mann, D L

1997-02-21

To determine whether activation of the neutral sphingomyelinase pathway was responsible for the immediate (<30 min) negative inotropic effects of tumor necrosis factor-alpha (TNF-alpha), we examined sphingosine levels in diluent and TNF-alpha-stimulated cardiac myocytes. TNF-alpha stimulation of adult feline cardiac myocytes provoked a rapid (<15 min) increase in the hydrolysis of [14C]sphingomyelin in cell-free extracts, as well as an increase in ceramide mass, consistent with cytokine-induced activation of the neutral sphingomyelinase pathway. High performance liquid chromatographic analysis of lipid extracts from TNF-alpha-stimulated cardiac myocytes showed that TNF-alpha stimulation produced a rapid (<30 min) increase in free sphingosine levels. Moreover, exogenous D-sphingosine mimicked the effects of TNF-alpha on intracellular calcium homeostasis, as well as the negative inotropic effects of TNF-alpha in isolated contracting myocytes; time course studies showed that exogenous D-sphingosine produced abnormalities in cell shortening that were maximal at 5 min. Finally, blocking sphingosine production using an inhibitor of ceramidase, n-oleoylethanolamine, completely abrogated the negative inotropic effects of TNF-alpha in isolated contracting cardiac myocytes. Additional studies employing biologically active ceramide analogs and sphingosine 1-phosphate suggested that neither the immediate precursor of sphingosine nor the immediate metabolite of sphingosine, respectively, were likely to be responsible for the immediate negative inotropic effects of TNF-alpha. Thus, these studies suggest that sphingosine mediates the immediate negative inotropic effects of TNF-alpha in isolated cardiac myocytes.

Suicide and war: the mediating effects of negative mood, posttraumatic stress disorder symptoms, and social support among army National Guard soldiers.

PubMed

Griffith, James

2012-08-01

The mediating effects of posttraumatic stress disorder (PTSD) symptoms, negative mood, and social support on the relationship of war experiences to suicidality were examined. The research literature suggested a sequence among study scales representing these constructs, which was then tested on survey data obtained from a sample of National Guard soldiers (N=4,546). Results from structural equation modeling suggested that war experiences may precipitate a sequence of psychological consequences leading to suicidality. However, suicidality may be an enduring behavioral health condition. War experiences showed no direct effects on postdeployment suicidality, rather its effect was indirect through PTSD symptoms and negative mood. War experiences were, however, predictive of PTSD symptoms, as would be expected. PSTD symptoms showed no direct effect on postdeployment suicidality, but showed indirect effects through negative mood. Results also suggested that suicidality is relatively persistent, at least during deployment and postdeployment. The percentage of those at risk for suicide was low both during and after deployment, with little association between suicidality and time since returning from deployment. Additionally, few soldiers were initially nonsuicidal and then reported such symptoms at postdeployment. Implications of relationships of both negative mood and combat trauma to suicidality are discussed, as well as possible mediating effects of both personal dispositions and social support on relationships of war experiences to PTSD, negative mood, and suicidality. © 2012 The American Association of Suicidology.

Sibship size and educational attainment. A joint test of the Confluence Model and the Resource Dilution Hypothesis

PubMed Central

Jæger, Mads Meier

2012-01-01

Studies on family background often explain the negative effect of sibship size on educational attainment by one of two theories: the Confluence Model (CM) or the Resource Dilution Hypothesis (RDH). However, as both theories – for substantively different reasons – predict that sibship size should have a negative effect on educational attainment most studies cannot distinguish empirically between the CM and the RDH. In this paper, I use the different theoretical predictions in the CM and RDH on the role of cognitive ability as a partial or complete mediator of the effect of sibship size to distinguish the two theories and to identify a unique RDH effect on educational attainment. Using sibling data from the Wisconsin Longitudinal Study (WLS) and a random effect Instrumental Variable model I find that, in addition to a negative effect on cognitive ability, sibship size also has a strong negative effect on educational attainment which is uniquely explained by the RDH. PMID:22468016

Relationships Between Stress, Negative Emotions, Resilience, and Smoking: Testing a Moderated Mediation Model.

PubMed

Wang, Yan; Chen, Xinguang; Gong, Jie; Yan, Yaqiong

2016-01-01

More effective tobacco prevention and cessation programs require in-depth understanding of the mechanism by which multiple factors interact with each other to affect smoking behaviors. Stress has long been recognized as a risk factor for smoking. However, the underlying mediation and moderation mechanisms are far from clear. The purpose of this study was to examine the role of negative emotions in mediating the link between stress and smoking and whether this indirect link was modified by resilience. Survey data were collected using audio computer-assisted self-interview (ACASI) from a large random sample of urban residents (n = 1249, mean age = 35.1, 45.3% male) in Wuhan, China. Perceived stress, negative emotions (anxiety, depression), resilience were measured with reliable instruments also validated in China. Self-reported smoking was validated with exhaled carbon monoxide. Mediation analysis indicated that two negative emotions fully mediated the link between stress and intensity of smoking (assessed by number of cigarettes smoked per day, effect =.082 for anxiety and.083 for depression) and nicotine dependence (assessed by DSM-IV standard, effect =.134 for anxiety and.207 for depression). Moderated mediation analysis demonstrated that the mediation effects of negative emotions were negatively associated with resilience. Results suggest resilience interacts with stress and negative emotions to affect the risk of tobacco use and nicotine dependence among Chinese adults. Further research with longitudinal data is needed to verify the findings of this study and to estimate the effect size of resilience in tobacco intervention and cessation programs.

Positive, negative, or all relative? Evaluative conditioning of ambivalence.

PubMed

Glaser, Tina; Woud, Marcella L; Labib Iskander, Michael; Schmalenstroth, Vera; Vo, Thuy My

2018-04-01

In evaluative conditioning (EC), the pairing of a positively or negatively valenced stimulus (US) with a neutral stimulus (CS) leads to a corresponding change in liking of the CS. EC research so far has concentrated on using unambiguously positive or negative USs. However, attitude objects are often ambivalent, i.e., can simultaneously possess positive and negative features. The present research investigated whether ambivalence can be evaluatively conditioned and whether contingency awareness moderates this effect. In two studies, positive, negative, neutral, and ambivalent USs were paired with affectively neutral CSs. Results showed standard EC effects that were moderated by contingency awareness. Most interestingly, EC effects were also obtained for the ambivalent USs, indicating that ambivalence can indeed be conditioned. However, contingency awareness seemed to play a lesser role in ambivalence conditioning. Ambivalence EC effects were obtained on subjective and objective direct measures of ambivalence as well as on a more indirect measure. Copyright © 2018 Elsevier B.V. All rights reserved.

A social relations model of observed family negativity and positivity using a genetically informative sample.

PubMed

Rasbash, Jon; Jenkins, Jennifer; O'Connor, Thomas G; Tackett, Jennifer; Reiss, David

2011-03-01

The goal of this study was to investigate individual and relationship influences on expressions of negativity and positivity in families. Parents and adolescents were observed in a round-robin design in a sample of 687 families. Data were analyzed using a multilevel social relations model. In addition, genetic contributions were estimated for actor effects. Children showed higher mean levels of negativity and lower mean levels of positivity as actors than did parents. Mothers were found to express and elicit higher mean levels of positivity and negativity than fathers. Actor effects were much stronger than partner effects, accounting for between 18%-39% of the variance depending on the actor and the outcome. Genetic (35%) and shared environmental (19%) influences explained a substantial proportion of the actor effect variance for negativity. Dyadic reciprocities were lowest in dyads with a high power differential (i.e., parent-child dyads) and highest for dyads with equal power (sibling and marital dyads). (c) 2011 APA, all rights reserved

Disability and Activity-related Emotion in Later Life: Are Effects Buffered by Intimate Relationship Support and Strain?

PubMed

Carr, Deborah; Cornman, Jennifer C; Freedman, Vicki A

2017-09-01

We use daily diary data from the Disability and Use of Time supplement to the 2013 Panel Study of Income Dynamics ( n = 1,162) to evaluate (1) the extent to which marital/partner support and strain moderate the effects of disability on five activity-related emotions (happiness, calm, sadness, frustration, worry) and overall negative and positive emotion among older married, cohabiting, and dating persons and (2) whether such patterns differ significantly by gender. Marital support buffers against negative emotions and increases feelings of calm among severely impaired women. By contrast, support intensifies negative emotions and decreases feelings of calm among severely impaired men. Relationship strain also intensifies the effect of severe impairment on men's frustration, sadness, worry, and negative mood but has negligible effects on the negative emotions of men with low impairment and women. Frequent support and criticism may threaten highly impaired older men's sense of autonomy and emotional well-being.

The Costs of Suppressing Negative Emotions and Amplifying Positive Emotions During Parental Caregiving.

PubMed

Le, Bonnie M; Impett, Emily A

2016-03-01

How do parents feel when they regulate their emotional expressions in ways that are incongruent with their genuine feelings? In an experimental study, parents reported experiencing lower authenticity, emotional well-being, relationship quality, and responsiveness to their children's needs when they recalled caregiving experiences in which they suppressed negative emotions and amplified positive emotions, relative to a control condition. In a 10-day daily experience study, parents tended to use both regulation strategies simultaneously. In addition, assessing their unique effects indicated that positive emotion amplification, but not negative emotion suppression, had an indirect effect on parental outcomes via authenticity, with negative emotion suppression no longer being costly. This indirect effect was dampened when accounting for care difficulty. In both studies, effects were independent of a child's mood. The current results suggest that parents' attempts to suppress negative and amplify positive emotions during child care can detract from their well-being and high-quality parent-child bonds. © 2016 by the Society for Personality and Social Psychology, Inc.

Negative-mass mitigation of Coulomb repulsion for terahertz undulator radiation of electron bunches

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

Balal, N.; Magory, E.; Bandurkin, I. V.

2015-10-19

It is proposed to utilize the effect of negative mass for stabilization of the effective axial size of very dense and short electron bunches produced by photo-injector guns by using combined undulator and strong uniform magnetic fields. It has been shown that in the “abnormal” regime, an increase in the electron energy leads to a decrease in the axial velocity of the electron; due to the negative-mass effect, the Coulomb repulsion of electrons leads to their attraction and formation of a fairly stable and compact bunch “nucleus.” An undulator with a strong uniform magnetic field providing the negative-mass effect ismore » designed for an experimental source of terahertz radiation. The use of the negative-mass regime in this experiment should result in a long-pulse coherent spontaneous undulator emission from a short dense moderately relativistic (5.5 MeV) photo-injector electron bunch with a high (up to 20%) efficiency and a narrow frequency spectrum.« less

Rhesus factor modulation of effects of smoking and age on psychomotor performance, intelligence, personality profile, and health in Czech soldiers.

PubMed

Flegr, Jaroslav; Geryk, Jan; Volný, Jindra; Klose, Jiří; Cernochová, Dana

2012-01-01

Rhesus-positive and rhesus-negative persons differ in the presence-absence of highly immunogenic RhD protein on the erythrocyte membrane. This protein is a component of NH(3) or CO(2) pump whose physiological role is unknown. Several recent studies have shown that RhD positivity protects against effects of latent toxoplasmosis on motor performance and personality. It is not known, however, whether the RhD phenotype modifies exclusively the response of the body to toxoplasmosis or whether it also influences effects of other factors. In the present cohort study, we searched for the effects of age and smoking on performance, intelligence, personality and self-estimated health and wellness in about 3800 draftees. We found that the positive effect of age on performance and intelligence was stronger in RhD-positive soldiers, while the negative effect of smoking on performance and intelligence was of similar size regardless of the RhD phenotype. The effect of age on four Cattell's personality factors, i.e., dominance (E), radicalism (Q(1)), self-sentiment integration (Q(3)), and ergic tension (Q(4)), and on Cloninger's factor reward dependency (RD) was stronger for RhD-negative than RhD-positive subjects, while the effect of smoking on the number of viral and bacterial diseases was about three times stronger for RhD-negative than RhD-positive subjects. RhD phenotype modulates the influence not only of latent toxoplasmosis, but also of at least two other potentially detrimental factors, age and smoking, on human behavior and physiology. The negative effect of smoking on health (estimated on the basis of the self-rated number of common viral and bacterial diseases in the past year) was much stronger in RhD-negative than RhD-positive subjects. It is critically needed to confirm the differences in health response to smoking between RhD-positive and RhD-negative subjects by objective medical examination in future studies.

Personality, negative affect coping, and drinking alone: a structural equation modeling approach to examine correlates of adolescent solitary drinking

PubMed Central

Creswell, Kasey G.; Chung, Tammy; Wright, Aidan G. C.; Clark, Duncan B.; Black, Jessica J.; Martin, Christopher S.

2015-01-01

Aims This study examined the personality traits of negative emotionality and constraint and the ability to resist drinking during negative affective states as correlates of solitary drinking in adolescence. We hypothesized that higher levels of negative emotionality and lower levels of constraint would predict solitary drinking and that these relationships would be mediated by the ability to resist drinking in response to negative emotions. Design Structural equation modeling was used to fit a path model from the personality traits of negative emotionality and constraint to solitary drinking status through intermediate effects on the ability to resist drinking during negative emotions using cross-sectional data. Setting Clinical and community settings in Pennsylvania, USA. Participants The sample included 761 adolescent drinkers (mean age = 17.1). Measurements Adolescents completed the Lifetime Drinking History, the Multidimensional Personality Questionnaire, the Constructive Thinking Inventory and the Situational Confidence Questionnaire. Findings The path model provided a good fit to the data. The association between trait negative emotionality and solitary drinking was fully mediated by adolescents' ability to resist drinking during negative affective states (b = 0.05, P = 0.01). In contrast, constraint had a direct effect on solitary drinking (odds ratio (OR) = 0.79, b = –0.23, P<0.01), as well as an indirect effect through the ability to resist drinking during negative affective states (b = –0.03, P = 0.02). Conclusions The ability to resist drinking while experiencing negative feelings or emotions may be an important underlying mechanism linking trait negative emotionality (a tendency toward depression, anxiety and poor reaction to stress) and constraint (lack of impulsiveness) to adolescent solitary drinking. PMID:25664806

Personality, negative affect coping, and drinking alone: a structural equation modeling approach to examine correlates of adolescent solitary drinking.

PubMed

Creswell, Kasey G; Chung, Tammy; Wright, Aidan G C; Clark, Duncan B; Black, Jessica J; Martin, Christopher S

2015-05-01

This study examined the personality traits of negative emotionality and constraint and the ability to resist drinking during negative affective states as correlates of solitary drinking in adolescence. We hypothesized that higher levels of negative emotionality and lower levels of constraint would predict solitary drinking and that these relationships would be mediated by the ability to resist drinking in response to negative emotions. Structural equation modeling was used to fit a path model from the personality traits of negative emotionality and constraint to solitary drinking status through intermediate effects on the ability to resist drinking during negative emotions using cross-sectional data. Clinical and community settings in Pennsylvania, USA. The sample included 761 adolescent drinkers (mean age = 17.1). Adolescents completed the Lifetime Drinking History, the Multidimensional Personality Questionnaire, the Constructive Thinking Inventory and the Situational Confidence Questionnaire. The path model provided a good fit to the data. The association between trait negative emotionality and solitary drinking was fully mediated by adolescents' ability to resist drinking during negative affective states (b = 0.05, P = 0.01). In contrast, constraint had a direct effect on solitary drinking (odds ratio (OR) = 0.79, b = -0.23, P<0.01), as well as an indirect effect through the ability to resist drinking during negative affective states (b = -0.03, P = 0.02). The ability to resist drinking while experiencing negative feelings or emotions may be an important underlying mechanism linking trait negative emotionality (a tendency toward depression, anxiety and poor reaction to stress) and constraint (lack of impulsiveness) to adolescent solitary drinking. © 2015 Society for the Study of Addiction.

Intelligence, Education, and Facets of Job Satisfaction.

ERIC Educational Resources Information Center

Ganzach, Yoav

2003-01-01

Analysis of two sets of National Longitudinal Survey data found that intelligence had a strong negative effect on intrinsic satisfaction, little effect on pay satisfaction, and positive association with desired job complexity, not expected pay. Education had a strong negative effect on pay satisfaction, little effect on intrinsic satisfaction, and…

Effects of Online Comments on Smokers’ Perception of Anti-Smoking Public Service Announcements

PubMed Central

Shi, Rui; Messaris, Paul; Cappella, Joseph N.

2014-01-01

On YouTube anti-smoking PSAs are widely viewed and uploaded; they also receive extensive commentary by viewers. This study examined whether such evaluative comments with or without uncivil expressions influence evaluations by subsequent viewers. Results showed PSAs with positive (i.e. anti-smoking) comments were perceived by smokers as more effective than PSAs with negative (pro smoking) comments. Smokers in the no comment condition gave the highest perceived effectiveness score to PSAs. Smokers’ readiness to quit smoking moderated the effect of comments on PSA evaluation. Smokers reading negative uncivil comments reported more negative attitude toward quitting and a lower level of perceived risk of smoking than those reading negative civil comments but positive civil and positive uncivil comments didn't elicit different responses. PMID:25561825

Effects of Online Comments on Smokers' Perception of Anti-Smoking Public Service Announcements.

PubMed

Shi, Rui; Messaris, Paul; Cappella, Joseph N

2014-07-01

On YouTube anti-smoking PSAs are widely viewed and uploaded; they also receive extensive commentary by viewers. This study examined whether such evaluative comments with or without uncivil expressions influence evaluations by subsequent viewers. Results showed PSAs with positive (i.e. anti-smoking) comments were perceived by smokers as more effective than PSAs with negative (pro smoking) comments. Smokers in the no comment condition gave the highest perceived effectiveness score to PSAs. Smokers' readiness to quit smoking moderated the effect of comments on PSA evaluation. Smokers reading negative uncivil comments reported more negative attitude toward quitting and a lower level of perceived risk of smoking than those reading negative civil comments but positive civil and positive uncivil comments didn't elicit different responses.

I think therefore I om: cognitive distortions and coping style as mediators for the effects of mindfulness meditation on anxiety, positive and negative affect, and hope.

PubMed

Sears, Sharon; Kraus, Sue

2009-06-01

This study examined cognitive distortions and coping styles as potential mediators for the effects of mindfulness meditation on anxiety, negative affect, positive affect, and hope in college students. Our pre- and postintervention design had four conditions: control, brief meditation focused on attention, brief meditation focused on loving kindness, and longer meditation combining both attentional and loving kindness aspects of mindfulness. Each group met weekly over the course of a semester. Longer combined meditation significantly reduced anxiety and negative affect and increased hope. Changes in cognitive distortions mediated intervention effects for anxiety, negative affect, and hope. Further research is needed to determine differential effects of types of meditation. Copyright 2009 Wiley Periodicals, Inc.

Neural circuits associated with positive and negative self-appraisal.

PubMed

Brühl, A B; Rufer, M; Kaffenberger, T; Baur, V; Herwig, U

2014-04-18

Self-worth is particularly influenced by self-appraisal, which is negatively biased in many psychiatric disorders. Positive and negative self-appraisals also shape current emotional states or even evoke defensive reactions, when they are incongruent with a subject's current state. Prior studies have mainly used externally given evaluative appraisals. In this study, 30 subjects used individual negative and positive self-appraisals during functional magnetic resonance imaging. We additionally investigated the effects of such self-appraisals onto the subsequent perception of photos of the individual subjects. Both self-appraisal conditions activated dorsomedial and dorsolateral prefrontal cortex compared to the neutral condition. Positive self-appraisal evoked stronger activity than negative self-appraisal in the amygdala, ventral striatum and anterior cingulate cortex, whereas negative self-appraisal was associated with increased activity in the occipital regions. Positive self-appraisal had no effect on the perception of a photo of oneself, whereas negative appraisal increased activity in the anterior insula and parietal regions. Overall, positive self-appraisal activated more emotion-related brain regions, whereas negative self-appraisal had a relatively stronger influence on perception-related brain activity. These findings could on the one hand explain the effect of negative self-appraisal on the behavior in the real world and on the other hand support a stronger focus of psychotherapy on enhancing positive self-appraisals. Copyright © 2014 IBRO. Published by Elsevier Ltd. All rights reserved.

Negative Academic Emotion and Psychological Well-being in Chinese Rural-to-Urban Migrant Adolescents: Examining the Moderating Role of Cognitive Reappraisal

PubMed Central

Wang, Daoyang; Li, Shuting; Hu, Mingming; Dong, Dan; Tao, Sha

2017-01-01

The study aimed to explore the relationship among negative academic emotions (e.g., anxiety, shame, anger, boredom, hopelessness, disappointment, and hatred), psychological well-being (including life vitality, health concern, altruism commitment, self-value, friendly relationship, and personal development), and cognitive reappraisal in rural-to-urban migrant adolescents in China. Specifically, it was hypothesized that the relationship between psychological well-being and negative academic emotions is moderated by cognitive reappraisal. A total of 311 migrant adolescents aged 14–20 years were selected, including 132 boys and 179 girls. Results of a regression analysis showed that cognitive reappraisal (positive) and negative academic emotions were significant predictors of psychological well-being. The interaction effect between cognitive reappraisal and negative academic emotion was also a significant predictor of psychological well-being. In the simple slope analysis the group with a below average cognitive reappraisal score the negative academic emotions were associated with lower psychological well-being, whereas in the group with above average cognitive reappraisal the effect of negative academic emotions on psychological well-being was not significant. However, for those with a cognitive reappraisal score of 1 standard deviation above the average, the effect of negative academic emotions on psychological well-being was not significant. These results suggest that cognitive reappraisal was a significant moderator in the relationship between negative academic emotion and psychological well-being. PMID:28824495

Negative Academic Emotion and Psychological Well-being in Chinese Rural-to-Urban Migrant Adolescents: Examining the Moderating Role of Cognitive Reappraisal.

PubMed

Wang, Daoyang; Li, Shuting; Hu, Mingming; Dong, Dan; Tao, Sha

2017-01-01

The study aimed to explore the relationship among negative academic emotions (e.g., anxiety, shame, anger, boredom, hopelessness, disappointment, and hatred), psychological well-being (including life vitality, health concern, altruism commitment, self-value, friendly relationship, and personal development), and cognitive reappraisal in rural-to-urban migrant adolescents in China. Specifically, it was hypothesized that the relationship between psychological well-being and negative academic emotions is moderated by cognitive reappraisal. A total of 311 migrant adolescents aged 14-20 years were selected, including 132 boys and 179 girls. Results of a regression analysis showed that cognitive reappraisal (positive) and negative academic emotions were significant predictors of psychological well-being. The interaction effect between cognitive reappraisal and negative academic emotion was also a significant predictor of psychological well-being. In the simple slope analysis the group with a below average cognitive reappraisal score the negative academic emotions were associated with lower psychological well-being, whereas in the group with above average cognitive reappraisal the effect of negative academic emotions on psychological well-being was not significant. However, for those with a cognitive reappraisal score of 1 standard deviation above the average, the effect of negative academic emotions on psychological well-being was not significant. These results suggest that cognitive reappraisal was a significant moderator in the relationship between negative academic emotion and psychological well-being.

Negative health system effects of Global Fund's investments in AIDS, tuberculosis and malaria from 2002 to 2009: systematic review.

PubMed

Car, Josip; Paljärvi, Tapio; Car, Mate; Kazeem, Ayodele; Majeed, Azeem; Atun, Rifat

2012-10-01

By using the Global Fund as a case example, we aim to critically evaluate the evidence generated from 2002 to 2009 for potential negative health system effects of Global Health Initiatives (GHI). Systematic review of research literature. Developing Countries. All interventions potentially affecting health systems that were funded by the Global Fund. Negative health system effects of Global Fund investments as reported by study authors. We identified 24 studies commenting on adverse effects on health systems arising from Global Fund investments. Sixteen were quantitative studies, six were qualitative and two used both quantitative and qualitative methods, but none explicitly stated that the studies were originally designed to capture or to assess health system effects (positive or negative). Only seemingly anecdotal evidence or authors' perceptions/interpretations of circumstances could be extracted from the included studies. This study shows that much of the currently available evidence generated between 2002 and 2009 on GHIs potential negative health system effects is not of the quality expected or needed to best serve the academic or broader community. The majority of the reviewed research did not fulfil the requirements of rigorous scientific evidence.

The effectiveness of different approaches to media literacy in modifying adolescents' responses to alcohol.

PubMed

Chen, Yi-Chun Yvonnes

2013-01-01

Fearing the negative effect that alcohol advertising might have on adolescents' receptiveness to the consumption of alcohol, health educators have used media literacy as an effective strategy to mitigate the effect of these messages in the media. The present study applied parental mediation to the design and evaluations of a media literacy curriculum that targets alcohol decision-making processes illustrated in the message interpretation process model. The authors conducted a pretest-posttest quasi-experiment of 171 adolescents to examine the effect of a negative evaluative approach and a balanced evaluative approach (a combination of negative and positive evaluative strategies) to media literacy on modifying adolescents' responses to alcohol messages. Results showed that different media literacy approaches had varying degrees of effectiveness on adolescent boys and girls. After receiving a negative media literacy lesson, adolescent boys regarded television characters as less realistic and believed that drinking alcohol had negative consequences. In contrast, adolescent girls benefited more from a balanced evaluative approach as their media skepticism attitude was enhanced. Results suggest that health educators should choose tailored pedagogical approaches that are based on gender to improve decision making regarding alcohol consumption.

An African grassland responds similarly to long-term fertilization to the Park Grass experiment.

PubMed

Ward, David; Kirkman, Kevin; Tsvuura, Zivanai

2017-01-01

We compared the results of a long-term (65 years) experiment in a South African grassland with the world's longest-running ecological experiment, the Park Grass study at Rothamsted, U.K. The climate is warm and humid in South Africa and cool and temperate in England. The African grassland has been fertilized with two forms of nitrogen applied at four levels, phosphorus and lime in a crossed design in 96 plots. In 1951, about 84% of plant cover consisted of Themeda triandra, Tristachya leucothrix and Setaria nigrirostris. Currently, the dominant species are Panicum maximum, Setaria sphacelata and Eragrostis curvula, making up 71% of total biomass. As in the Park Grass experiment, we found a significant (additive) interaction effect on ANPP of nitrogen and phosphorus, and a (marginally significant) negative correlation between ANPP and species richness. Unlike the Park Grass experiment, there was no correlation between ANPP and species richness when pH was included as a covariate. There was also a significant negative effect of nitrogen amount and nitrogen form and a positive effect of lime on species richness and species diversity. Soil pH had an important effect on species richness. Liming was insufficient to balance the negative effects on species richness of nitrogen fertilization. There was a significant effect of pH on biomass of three abundant species. There were also significant effects of light on the biomass of four species, with only Panicum maximum having a negative response to light. In all of the abundant species, adding total species richness and ANPP to the model increased the amount of variance explained. The biomass of Eragrostis curvula and P. maximum were negatively correlated with species richness while three other abundant species increased with species richness, suggesting that competition and facilitation were active. Consistent with the results from the Park Grass and other long-term fertilization experiments of grasslands, we found a positive effect of soil pH and a negative effect of nitrogen amount on species richness, a more acutely negative effect on species richness of acidic ammonium sulphate fertilizer than limestone ammonium nitrate, a negative relationship between species richness and biomass, and a positive effect on species richness of lime interacting with nitrogen.

Negative Capacitance in BaTiO3/BiFeO3 Bilayer Capacitors.

PubMed

Hou, Ya-Fei; Li, Wei-Li; Zhang, Tian-Dong; Yu, Yang; Han, Ren-Lu; Fei, Wei-Dong

2016-08-31

Negative capacitances provide an approach to reduce heat generations in field-effect transistors during the switch processes, which contributes to further miniaturization of the conventional integrated circuits. Although there are many studies about negative capacitances using ferroelectric materials, the direct observation of stable ferroelectric negative capacitances has rarely been reported. Here, we put forward a dc bias assistant model in bilayer capacitors, where one ferroelectric layer with large dielectric constant and the other ferroelectric layer with small dielectric constant are needed. Negative capacitances can be obtained when external dc bias electric fields are larger than a critical value. Based on the model, BaTiO3/BiFeO3 bilayer capacitors are chosen as study objects, and negative capacitances are observed directly. Additionally, the upward self-polarization effect in the ferroelectric layer reduces the critical electric field, which may provide a method for realizing zero and/or small dc bias assistant negative capacitances.

Helping employees sleep well: Effects of cognitive behavioral therapy for insomnia on work outcomes.

PubMed

Barnes, Christopher M; Miller, Jared A; Bostock, Sophie

2017-01-01

Drawing from recent research advances indicating the harmful effects of insomnia on negative affect, job satisfaction, self-control, organizational citizenship behavior, and interpersonal deviance, we hypothesized that treating insomnia with Internet based cognitive behavior therapy for insomnia would lead to improvements in these outcomes. In a field experiment with a randomized wait-list control group, we found that treatment had a beneficial direct effect on negative affect, job satisfaction, and self-control. Moreover, the effect of treatment on job satisfaction was mediated by negative affect. We were not able to detect a direct effect of treatment on organizational citizenship behavior or interpersonal deviance. However, treatment had a beneficial indirect effect on organizational citizenship behavior through the mediators of negative affect and job satisfaction, and a beneficial indirect effect on interpersonal deviance through the mediator of self-control. These results move the applied psychology literature on insomnia beyond simply pointing out problematic effects of employee insomnia to providing evidence of a partial solution to such effects. (PsycINFO Database Record (c) 2017 APA, all rights reserved).

Local cardiac effects of substance P: roles of acetylcholine and noradrenaline.

PubMed Central

Chiao, H; Caldwell, R W

1995-01-01

1. The local cardiac actions of substance P were examined in isolated perfused hearts and atria of the guinea-pig. 2. In both hearts and right atria, substance P caused negative inotropic and chronotropic effects. 3. Atropine (10(-6) M) or depletion of acetylcholine, by electrical stimulation and hemicholinium-3 perfusion, significantly attenuated the negative inotropic and chronotropic effects of substance P. alpha- and beta-adrenoceptor blockade by nadolol and phentolamine (10(-6) M each) did not prevent the negative inotropic and chronotropic effects of substance P. This indicates that cholinergic neurones, but not adrenergic neurones, partially mediate the effects of substance P. 4. There was no significant difference in the effects of substance P observed between groups with acetylcholine depletion and with cholinoceptor blockade. This suggests that substance P elicits its effects mainly through release of acetylcholine. 5. These results indicate that substance P has negative inotropic and chronotropic effects in guinea-pig hearts and right atria mediated partly by release of acetylcholine. Substance P also appears to have direct effects on cardiac tissue. PMID:7533612

Effect of Art Production on Negative Mood and Anxiety for Adults in Treatment for Substance Abuse

ERIC Educational Resources Information Center

Laurer, Mattye; van der Vennet, Renée

2015-01-01

This study investigated whether art production or viewing and sorting art reproductions would be more effective in reducing negative mood and anxiety for 28 adults with substance use disorders. Participants were randomly assigned to one of two groups and completed pre- and posttest measures of negative mood and anxiety The hypothesis that art…

Child Temperament Moderates Effects of Parent-Child Mutuality on Self-Regulation: A Relationship-Based Path for Emotionally Negative Infants

ERIC Educational Resources Information Center

Kim, Sanghag; Kochanska, Grazyna

2012-01-01

This study examined infants' negative emotionality as moderating the effect of parent-child mutually responsive orientation (MRO) on children's self-regulation (n = 102). Negative emotionality was observed in anger-eliciting episodes and in interactions with parents at 7 months. MRO was coded in naturalistic interactions at 15 months.…

That's not funny! - But it should be: effects of humorous emotion regulation on emotional experience and memory.

PubMed

Kugler, Lisa; Kuhbandner, Christof

2015-01-01

Previous research has shown that humorous reappraisal can reduce elicited negative emotions, suggesting that humor may be a functional strategy to cope with emotionally negative situations. However, the effect of humorous reappraisal on later memory about the emotion-eliciting situation is currently unknown, although this is crucial for more adaptive responding in future situations. To address this issue, we examined the effects of humorous reappraisal on both emotional experience and memory, compared to non-humorous rational reappraisal and a non-reappraisal control condition. Replicating previous findings, humorous reappraisal reduced evoked negative valence and arousal levels very effectively, and the down-regulation of experienced negative emotions was even more pronounced after humorous compared to rational reappraisal. Regarding later memory for emotion-eliciting stimuli, both humorous and rational reappraisal reduced free recall, but recognition memory was unaffected, with memory strength being stronger after humorous than after rational reappraisal. These results indicate that humor seems to be indeed an optimal strategy to cope with negative situations because humor can help us to feel better when confronted with negative stimuli, but still allows us to retrieve stimulus information later when afforded to do so by the presence of appropriate contextual features.

[Effect of workplace bullying on posttraumatic stress disorder in nursing staff].

PubMed

Sun, Y Q; Ge, Y X; Ke, Z W; Li, Y Y; Jin, Q X; Lu, Y F

2018-01-20

Objective: To investigate the relationship between workplace bullying and posttraumatic stress disorder (PTSD) in nursing staff, and to analyze the role of psychological capital between workplace bullying and PTSD. Methods: From December 2014 to June 2015, convenience sampling was used to collect 496 nurses from 5 grade A tertiary hospitals in a province of China. Their workplace bullying, psychological capital, and PTSD status were assessed using the Negative Acts Questionnaire, Psychological Capital Questionnaire, and Posttraumatic Stress Disorder Self-Rating Scale, respectively. The correlation between variables was analyzed using a structural equation model. Results: Among these nurses, the scores of negative acts, psychological capital, and PTSD were 37.15±12.83, 78.81±16.54, and 34.56±12.52, respectively. The score on each dimension of negative acts was positively correlated with that on each dimension of PTSD ( P <0.01) ; the score on each dimension of psychological capital was negatively correlated with that on each dimension of PTSD and negative acts ( P <0.01). Negative acts had a positive predictive effect on PTSD ( β =0.539, P <0.01) , which was reduced after inclusion of psychological capital ( β =0.513, P <0.01). The path coefficient was 0.62 for the effect of negative acts on PTSD, -0.18 for the effect of negative acts on psychological capital, and -0.11 for the effect of psychological capital on PTSD ( P <0.05) . Conclusion: Workplace bullying is a predictive factor for PTSD, and psychological capital plays a mediating role between workplace bullying and PTSD. The manager should reduce workplace bullying to improve the psychological capital in nursing staff and to prevent and reduce PTSD.

Investigation of Dusts Effect and Negative Ion in DC Plasmas by Electric Probes

NASA Astrophysics Data System (ADS)

Oh, Hye Taek; Kang, Inje; Bae, Min-Keun; Park, Insun; Lee, Seunghwa; Jeong, Seojin; Chung, Kyu-Sun

2017-10-01

Dust is typically negatively charged by electron attachment whose thermal velocities are fast compared to that of the heavier ions. The negatively charged particles can play a role of negative ions which affect the quasi-neutrality of background plasma. To investigate effect of metal dusts and negative ion on plasma and materials, metal dusts are injected into background Ar plasma which is generated by tungsten filament using dust dispenser on Cubical Plasma Device (CPD). The CPD has following conditions: size =24x24x24cm3, plasma source =DC filament plasma (ne 1x10x1010, Te 2eV), background gas =Ar, dusts =tungsten powder (diameter 1.89micron). The dust dispenser is developed to quantitate of metal dust by ultrasonic transducer. Electronegative plasmas are generated by adding O2 + Ar plasma to compare negative ion and dust effect. A few grams of micron-sized dusts are placed in the dust dispenser which is located at the upper side of the Cubical Plasma Device. The falling particles by dust dispenser are mainly charged up by the collection of the background plasma. The change in parameters due to negative ion production are characterized by measuring the floating and plasma potential, electron temperature and negative ion density using electric probes.

Do negative emotions expressed during follow-up consultations with adolescent survivors of childhood cancer reflect late effects?

PubMed

Mellblom, Anneli V; Ruud, Ellen; Loge, Jon Håvard; Lie, Hanne C

2017-11-01

To explore whether negative emotions expressed by adolescent cancer survivors during follow-up consultations were associated with potential late effects (persisting disease or treatment-related health problems). We video-recorded 66 follow-up consultations between 10 pediatricians and 66 adolescent survivors of leukemia, lymphoma or stem-cell transplantations. In transcripts of the recordings, we identified utterances coded as both 1) expressions of negative emotions (VR-CoDES), and 2) late effect-related discussions. Principles of thematic content analysis were used to investigate associations between the two. Of the 66 video-recorded consultations, 22 consultations contained 56 (49%) utterances coded as both emotional concerns and discussions of potential late effects. Negative emotions were most commonly associated with late effects such as fatigue ("I'm struggling with not having energy"), psychosocial distress ("When I touch this (scar) I become nauseous"), pain ("I'm wondering how long I am going to have this pain?"), and treatment-related effects on physical appearance ("Am I growing?"). Negative emotions expressed by adolescent cancer survivors during follow-up consultations were frequently associated with potential late effects. These late effects were not the medically most serious ones, but reflected issues affecting the adolescents' daily life. Eliciting and exploring patients' emotional concerns serve as means to obtain clinically relevant information regarding potential late effect and to provide emotional support. Copyright © 2017 Elsevier B.V. All rights reserved.

Testing a model of depression among Thai adolescents.

PubMed

Vatanasin, Duangjai; Thapinta, Darawan; Thompson, Elaine Adams; Thungjaroenkul, Petsunee

2012-11-01

This predictive correlational study was designed to test a comprehensive model of depression for Thai adolescents. This sample included 800 high school students in Chiang Mai, Thailand. Data were collected using self-reported measures of depression, negative automatic thoughts, effective social problem solving, ineffective social problem solving, rumination, parental care, parental overprotection, and negative life events. Structural equation modeling revealed that negative automatic thoughts, effective and ineffective social problem solving mediated the effects of rumination, negative life events, and parental care and overprotection on adolescent depression. These findings provide new knowledge about identified factors and the mechanisms of their influence on depression among Thai adolescents, which are appropriate for targeting preventive interventions. © 2012 Wiley Periodicals, Inc.

Promoting walking in older adults: Perceived neighborhood walkability influences the effectiveness of motivational messages.

PubMed

Notthoff, Nanna; Carstensen, Laura L

2017-06-01

Positively framed messages seem to promote walking in older adults better than negatively framed messages. This study targeted elderly people in communities unfavorable to walking. Walking was measured with pedometers during baseline (1 week) and intervention (4 weeks). Participants ( n = 74) were informed about either the benefits of walking or the negative consequences of not walking. Perceived neighborhood walkability was assessed with a modified version of the Neighborhood Walkability Scale. When perceived walkability was high, positively framed messages were more effective than negatively framed messages in promoting walking; when perceived walkability was low, negatively framed messages were comparably effective to positively framed messages.

Effects of negative gate-bias stress on the performance of solution-processed zinc-oxide transistors

NASA Astrophysics Data System (ADS)

Kim, Dongwook; Lee, Woo-Sub; Shin, Hyunji; Choi, Jong Sun; Zhang, Xue; Park, Jaehoon; Hwang, Jaeeun; Kim, Hongdoo; Bae, Jin-Hyuk

2014-08-01

We studied the effects of negative gate-bias stress on the electrical characteristics of top-contact zinc-oxide (ZnO) thin-film transistors (TFTs), which were fabricated by spin coating a ZnO solution onto a silicon-nitride gate dielectric layer. The negative gate-bias stress caused characteristic degradations in the on-state currents and the field-effect mobility of the fabricated ZnO TFTs. Additionally, a decrease in the off-state currents and a positive shift in the threshold voltage occurred with increasing stress time. These results indicate that the negative gate-bias stress caused an injection of electrons into the gate dielectric, thereby deteriorating the TFT's performance.

[Antimicrobial therapy in severe infections with multidrug-resistant Gram-negative bacterias].

PubMed

Duszyńska, Wiesława

2010-01-01

Multidrug-resistant Gram-negative bacteria pose a serious and rapidly emerging threat to patients in healthcare settings, and are especially prevalent and problematic in intensive therapy units. Recently, the emergence of pandrug-resistance in Gram-negative bacteria poses additional concerns. This review examines the clinical impact and epidemiology of multidrug-resistant Gram-negative bacteria as a cause of increased morbidity and mortality among ITU patients. Beta-lactamases, cephalosporinases and carbapenemases play the most important role in resistance to antibiotics. Despite the tendency to increased resistance, carbapenems administered by continuous infusion remain the most effective drugs in severe sepsis. Drug concentration monitoring, albeit rarely used in practice, is necessary to ensure an effective therapeutic effect.

Comparing the effects of negative and mixed emotional messages on predicted occasional excessive drinking.

PubMed

Carrera, Pilar; Caballero, Amparo; Muñoz, Dolores

2008-01-01

In this work we present two types of emotional message, negative (sadness) versus mixed (joy and sadness), with the aim of studying their differential effect on attitude change and the probability estimated by participants of repeating the behavior of occasional excessive drinking in the near future. The results show that for the group of participants with moderate experience in this behavior the negative message, compared to the mixed one, is associated with higher probability of repeating the risk behavior and a less negative attitude toward it. These results suggest that mixed emotional messages (e.g. joy and sadness messages) could be more effective in campaigns for the prevention of this risk behavior.

Do managed bees have negative effects on wild bees?: A systematic review of the literature

PubMed Central

Gratton, Claudio

2017-01-01

Managed bees are critical for crop pollination worldwide. As the demand for pollinator-dependent crops increases, so does the use of managed bees. Concern has arisen that managed bees may have unintended negative impacts on native wild bees, which are important pollinators in both agricultural and natural ecosystems. The goal of this study was to synthesize the literature documenting the effects of managed honey bees and bumble bees on wild bees in three areas: (1) competition for floral and nesting resources, (2) indirect effects via changes in plant communities, including the spread of exotic plants and decline of native plants, and (3) transmission of pathogens. The majority of reviewed studies reported negative effects of managed bees, but trends differed across topical areas. Of studies examining competition, results were highly variable with 53% reporting negative effects on wild bees, while 28% reported no effects and 19% reported mixed effects (varying with the bee species or variables examined). Equal numbers of studies examining plant communities reported positive (36%) and negative (36%) effects, with the remainder reporting no or mixed effects. Finally, the majority of studies on pathogen transmission (70%) reported potential negative effects of managed bees on wild bees. However, most studies across all topical areas documented the potential for impact (e.g. reporting the occurrence of competition or pathogens), but did not measure direct effects on wild bee fitness, abundance, or diversity. Furthermore, we found that results varied depending on whether managed bees were in their native or non-native range; managed bees within their native range had lesser competitive effects, but potentially greater effects on wild bees via pathogen transmission. We conclude that while this field has expanded considerably in recent decades, additional research measuring direct, long-term, and population-level effects of managed bees is needed to understand their potential impact on wild bees. PMID:29220412

Do managed bees have negative effects on wild bees?: A systematic review of the literature.

PubMed

Mallinger, Rachel E; Gaines-Day, Hannah R; Gratton, Claudio

2017-01-01

Managed bees are critical for crop pollination worldwide. As the demand for pollinator-dependent crops increases, so does the use of managed bees. Concern has arisen that managed bees may have unintended negative impacts on native wild bees, which are important pollinators in both agricultural and natural ecosystems. The goal of this study was to synthesize the literature documenting the effects of managed honey bees and bumble bees on wild bees in three areas: (1) competition for floral and nesting resources, (2) indirect effects via changes in plant communities, including the spread of exotic plants and decline of native plants, and (3) transmission of pathogens. The majority of reviewed studies reported negative effects of managed bees, but trends differed across topical areas. Of studies examining competition, results were highly variable with 53% reporting negative effects on wild bees, while 28% reported no effects and 19% reported mixed effects (varying with the bee species or variables examined). Equal numbers of studies examining plant communities reported positive (36%) and negative (36%) effects, with the remainder reporting no or mixed effects. Finally, the majority of studies on pathogen transmission (70%) reported potential negative effects of managed bees on wild bees. However, most studies across all topical areas documented the potential for impact (e.g. reporting the occurrence of competition or pathogens), but did not measure direct effects on wild bee fitness, abundance, or diversity. Furthermore, we found that results varied depending on whether managed bees were in their native or non-native range; managed bees within their native range had lesser competitive effects, but potentially greater effects on wild bees via pathogen transmission. We conclude that while this field has expanded considerably in recent decades, additional research measuring direct, long-term, and population-level effects of managed bees is needed to understand their potential impact on wild bees.

Primary prevention research: a preliminary review of program outcome studies.

PubMed

Schaps, E; Churgin, S; Palley, C S; Takata, B; Cohen, A Y

1980-07-01

This article reviews 35 drug abuse prevention program evaluations employing drug-specific outcome measures. Many of these evaluations assessed the effects of "new generation" prevention strategies: affective, peer-oriented, and multidimensional approaches. Only 14 studies evaluated purely informational programs. Evaluations were analyzed to ascertain (1) characteristics of the programs under study, (2) characteristics of the research designs, and (3) patterns among findings. This review provides some evidence that the newer prevention strategies may produce more positive and fewer negative outcomes than did older drug information approaches. Over 70% of the programs using the newer strategies produced some positive effects; only 29% showed negative effects. In contrast, 46% of informational programs showed positive effects; 46% showed negative effects. These findings must be approached with great caution, since the research was frequently scientifically inadequate, and since rigor of research was negatively correlated with intensity and duration of program services.

The Effects of a Distracting N-Back Task on Recognition Memory Are Reduced by Negative Emotional Intensity

PubMed Central

Buratto, Luciano G.; Pottage, Claire L.; Brown, Charity; Morrison, Catriona M.; Schaefer, Alexandre

2014-01-01

Memory performance is usually impaired when participants have to encode information while performing a concurrent task. Recent studies using recall tasks have found that emotional items are more resistant to such cognitive depletion effects than non-emotional items. However, when recognition tasks are used, the same effect is more elusive as recent recognition studies have obtained contradictory results. In two experiments, we provide evidence that negative emotional content can reliably reduce the effects of cognitive depletion on recognition memory only if stimuli with high levels of emotional intensity are used. In particular, we found that recognition performance for realistic pictures was impaired by a secondary 3-back working memory task during encoding if stimuli were emotionally neutral or had moderate levels of negative emotionality. In contrast, when negative pictures with high levels of emotional intensity were used, the detrimental effects of the secondary task were significantly attenuated. PMID:25330251

The effects of a distracting N-back task on recognition memory are reduced by negative emotional intensity.

PubMed

Buratto, Luciano G; Pottage, Claire L; Brown, Charity; Morrison, Catriona M; Schaefer, Alexandre

2014-01-01

Memory performance is usually impaired when participants have to encode information while performing a concurrent task. Recent studies using recall tasks have found that emotional items are more resistant to such cognitive depletion effects than non-emotional items. However, when recognition tasks are used, the same effect is more elusive as recent recognition studies have obtained contradictory results. In two experiments, we provide evidence that negative emotional content can reliably reduce the effects of cognitive depletion on recognition memory only if stimuli with high levels of emotional intensity are used. In particular, we found that recognition performance for realistic pictures was impaired by a secondary 3-back working memory task during encoding if stimuli were emotionally neutral or had moderate levels of negative emotionality. In contrast, when negative pictures with high levels of emotional intensity were used, the detrimental effects of the secondary task were significantly attenuated.

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

Cao, Jianjun; Shen, Dongyi; Feng, Yaming

Negative refraction has attracted much interest for its promising capability in imaging applications. Such an effect can be implemented by negative index meta-materials, however, which are usually accompanied by high loss and demanding fabrication processes. Recently, alternative nonlinear approaches like phase conjugation and four wave mixing have shown advantages of low-loss and easy-to-implement, but associated problems like narrow accepting angles can still halt their practical applications. Here, we demonstrate theoretically and experimentally a scheme to realize negative refraction by nonlinear difference frequency generation with wide tunability, where a thin Beta barium borate slice serves as a negative refraction layer bendingmore » the input signal beam to the idler beam at a negative angle. Furthermore, we realize optical focusing effect using such nonlinear negative refraction, which may enable many potential applications in imaging science.« less

[SYMPTOMS OF NEGATIVE EFFECTS CUMULATION IN HUMANS AND ANIMALS UNDER THE ACTION OF G-LOADS OF VARYING DIRECTION IN CONTEXT OF AVIATION AND SPACE FLIGHTS].

PubMed

Kotovskaya, A R

2015-01-01

Author's and literary data are analyzed to evince symptoms of cumulation in humans and animals of the negative effects caused by g-forces of different directions experienced in aviation and space flights. The author cites evidence for the decisive importance of g-duration for the development of negative effects. Functional indices of g-tolerance do not rule out possible latent changes in visceral organs and body tissues.

Relations of spanking and other parenting characteristics to self-esteem and perceived fairness of parental discipline.

PubMed

Larzelere, R E; Klein, M; Schumm, W R; Alibrando, S A

1989-06-01

Punishment has long been a controversial topic in psychology, perhaps partly because its effects are different under different circumstances. This study used retrospective reports from college students to examine the effects of spanking, a common aversive punishment, on self-esteem and perceived fairness of parental discipline, while taking the effects of other parental characteristics into account. No parental characteristic interacted with the slightly negative effect of spanking on self-esteem and fairness. However, controlling for positive communication or for a parent-oriented motivation for spanking eliminated the negative effects of spanking, suggesting that the negative effects reflected use of spanking as a replacement for positive communication with the child.

Method effects: the problem with negatively versus positively keyed items.

PubMed

Lindwall, Magnus; Barkoukis, Vassilis; Grano, Caterina; Lucidi, Fabio; Raudsepp, Lennart; Liukkonen, Jarmo; Thøgersen-Ntoumani, Cecilie

2012-01-01

Using confirmatory factor analyses, we examined method effects on Rosenberg's Self-Esteem Scale (RSES; Rosenberg, 1965) in a sample of older European adults. Nine hundred forty nine community-dwelling adults 60 years of age or older from 5 European countries completed the RSES as well as measures of depression and life satisfaction. The 2 models that had an acceptable fit with the data included method effects. The method effects were associated with both positively and negatively worded items. Method effects models were invariant across gender and age, but not across countries. Both depression and life satisfaction predicted method effects. Individuals with higher depression scores and lower life satisfaction scores were more likely to endorse negatively phrased items.

Factors affecting plant growth in membrane nutrient delivery

NASA Technical Reports Server (NTRS)

Dreschel, T. W.; Wheeler, R. M.; Sager, J. C.; Knott, W. M.

1990-01-01

The development of the tubular membrane plant growth unit for the delivery of water and nutrients to roots in microgravity has recently focused on measuring the effects of changes in physical variables controlling solution availability to the plants. Significant effects of membrane pore size and the negative pressure used to contain the solution were demonstrated. Generally, wheat grew better in units with a larger pore size but equal negative pressure and in units with the same pore size but less negative pressure. Lettuce also exhibited better plant growth at less negative pressure.

Physical principles of the amplification of electromagnetic radiation due to negative electron masses in a semiconductor superlattice

NASA Astrophysics Data System (ADS)

Shorokhov, A. V.; Pyataev, M. A.; Khvastunov, N. N.; Hyart, T.; Kusmartsev, F. V.; Alekseev, K. N.

2015-02-01

In a superlattice placed in crossed static electric and magnetic fields, under certain conditions, the inversion of electron population can appear at which the average energy of electrons is above the middle of the mini-band and the effective mass of the electron is negative. This is the implementation of the negative effective mass amplifier and generator (NEMAG) in the superlattice. It can result in the amplification and generation of terahertz radiation even in the absence of negative differential conductivity.

Relation Between Mathematical Performance, Math Anxiety, and Affective Priming in Children With and Without Developmental Dyscalculia.

PubMed

Kucian, Karin; Zuber, Isabelle; Kohn, Juliane; Poltz, Nadine; Wyschkon, Anne; Esser, Günter; von Aster, Michael

2018-01-01

Many children show negative emotions related to mathematics and some even develop mathematics anxiety. The present study focused on the relation between negative emotions and arithmetical performance in children with and without developmental dyscalculia (DD) using an affective priming task. Previous findings suggested that arithmetic performance is influenced if an affective prime precedes the presentation of an arithmetic problem. In children with DD specifically, responses to arithmetic operations are supposed to be facilitated by both negative and mathematics-related primes (= negative math priming effect ).We investigated mathematical performance, math anxiety, and the domain-general abilities of 172 primary school children (76 with DD and 96 controls). All participants also underwent an affective priming task which consisted of the decision whether a simple arithmetic operation (addition or subtraction) that was preceded by a prime (positive/negative/neutral or mathematics-related) was true or false. Our findings did not reveal a negative math priming effect in children with DD. Furthermore, when considering accuracy levels, gender, or math anxiety, the negative math priming effect could not be replicated. However, children with DD showed more math anxiety when explicitly assessed by a specific math anxiety interview and showed lower mathematical performance compared to controls. Moreover, math anxiety was equally present in boys and girls, even in the earliest stages of schooling, and interfered negatively with performance. In conclusion, mathematics is often associated with negative emotions that can be manifested in specific math anxiety, particularly in children with DD. Importantly, present findings suggest that in the assessed age group, it is more reliable to judge math anxiety and investigate its effects on mathematical performance explicitly by adequate questionnaires than by an affective math priming task.

Relation Between Mathematical Performance, Math Anxiety, and Affective Priming in Children With and Without Developmental Dyscalculia

PubMed Central

Kucian, Karin; Zuber, Isabelle; Kohn, Juliane; Poltz, Nadine; Wyschkon, Anne; Esser, Günter; von Aster, Michael

2018-01-01

Many children show negative emotions related to mathematics and some even develop mathematics anxiety. The present study focused on the relation between negative emotions and arithmetical performance in children with and without developmental dyscalculia (DD) using an affective priming task. Previous findings suggested that arithmetic performance is influenced if an affective prime precedes the presentation of an arithmetic problem. In children with DD specifically, responses to arithmetic operations are supposed to be facilitated by both negative and mathematics-related primes (=negative math priming effect).We investigated mathematical performance, math anxiety, and the domain-general abilities of 172 primary school children (76 with DD and 96 controls). All participants also underwent an affective priming task which consisted of the decision whether a simple arithmetic operation (addition or subtraction) that was preceded by a prime (positive/negative/neutral or mathematics-related) was true or false. Our findings did not reveal a negative math priming effect in children with DD. Furthermore, when considering accuracy levels, gender, or math anxiety, the negative math priming effect could not be replicated. However, children with DD showed more math anxiety when explicitly assessed by a specific math anxiety interview and showed lower mathematical performance compared to controls. Moreover, math anxiety was equally present in boys and girls, even in the earliest stages of schooling, and interfered negatively with performance. In conclusion, mathematics is often associated with negative emotions that can be manifested in specific math anxiety, particularly in children with DD. Importantly, present findings suggest that in the assessed age group, it is more reliable to judge math anxiety and investigate its effects on mathematical performance explicitly by adequate questionnaires than by an affective math priming task. PMID:29755376

Hostile Attributional Bias, Negative Emotional Responding, and Aggression in Adults: Moderating Effects of Gender and Impulsivity

PubMed Central

Chen, Pan; Coccaro, Emil F.; Jacobson, Kristen C.

2012-01-01

The current study examined the main effects of hostile attributional bias (HAB) and negative emotional responding on a variety of aggressive behaviors in adults, including general aggression, physical aggression, relational aggression, and verbal aggression. Effects of both externalizing (anger) and internalizing (embarrassment/upset) negative emotions were considered. In addition, the moderating roles of gender and impulsivity on the effects of HAB and negative emotional responding were explored. Multilevel models were fitted to data from 2,749 adult twins aged 20–55 from the PennTwins cohort. HAB was positively associated with all four forms of aggression. There was also a significant interaction between impulsivity and HAB for general aggression. Specifically, the relationship between HAB and general aggression was only significant for individuals with average or above-average levels of impulsivity. Negative emotional responding was also found to predict all measures of aggression, although in different ways. Anger was positively associated with all forms of aggression, whereas embarrassment/upset predicted decreased levels of general, physical, and verbal aggression but increased levels of relational aggression. The associations between negative emotional responding and aggression were generally stronger for males than females. The current study provides evidence for the utility of HAB and negative emotional responding as predictors of adult aggression and further suggests that gender and impulsivity may moderate their links with aggression. PMID:24833604

Hostile attributional bias, negative emotional responding, and aggression in adults: moderating effects of gender and impulsivity.

PubMed

Chen, Pan; Coccaro, Emil F; Jacobson, Kristen C

2012-01-01

The current study examined the main effects of hostile attributional bias (HAB) and negative emotional responding on a variety of aggressive behaviors in adults, including general aggression, physical aggression, relational aggression, and verbal aggression. Effects of both externalizing (anger) and internalizing (embarrassment/upset) negative emotions were considered. In addition, the moderating roles of gender and impulsivity on the effects of HAB and negative emotional responding were explored. Multilevel models were fitted to data from 2,749 adult twins aged 20-55 from the PennTwins cohort. HAB was positively associated with all four forms of aggression. There was also a significant interaction between impulsivity and HAB for general aggression. Specifically, the relationship between HAB and general aggression was only significant for individuals with average or above-average levels of impulsivity. Negative emotional responding was also found to predict all measures of aggression, although in different ways. Anger was positively associated with all forms of aggression, whereas embarrassment/upset predicted decreased levels of general, physical, and verbal aggression but increased levels of relational aggression. The associations between negative emotional responding and aggression were generally stronger for males than females. The current study provides evidence for the utility of HAB and negative emotional responding as predictors of adult aggression and further suggests that gender and impulsivity may moderate their links with aggression. © 2011 Wiley Periodicals, Inc.

Inhibition of Return Is Modulated by Negative Stimuli: Evidence from Subliminal Perception.

PubMed

Pan, Fada; Wu, Xiaogang; Zhang, Li; Ou, Yuhong

2017-01-01

Inhibition of return (IOR) is considered as a "blindness mechanism" that emotional stimuli have no impact on it. Most previous studies suggested that IOR was not modulated by emotional cues. However, one key question they ignored was that only supraliminal presentation of emotional stimuli was used in their experiments. The present experiment is aimed at exploring the possible interaction between the IOR effect and subliminal emotional process. We manipulated three different kinds of valence strength of negative stimuli (high negative, HN; moderate negative, MN; low negative, LN) which were presented under the subliminal perception level and an event-related potentials (ERPs) recording was adopted. The results showed that, compared to MN and HN, the IOR effect triggered by peripheral cues was more significant for LN with aspects of behavioral and electrophysiological data (a reduction P1 effect, more negative on cued trials than on uncued trials for both early posterior Nd and Nd components). This indicated that IOR can be modulated by emotionally relevant stimuli. The automatic processing that was triggered by subliminally negative stimuli of peripheral cues had an influence on the shifting of spatial attention that was triggered by IOR. These two mechanisms may occur in the perceptual stage simultaneously.

Negativity Bias in Media Multitasking: The Effects of Negative Social Media Messages on Attention to Television News Broadcasts.

PubMed

Kätsyri, Jari; Kinnunen, Teemu; Kusumoto, Kenta; Oittinen, Pirkko; Ravaja, Niklas

2016-01-01

Television viewers' attention is increasingly more often divided between television and "second screens", for example when viewing television broadcasts and following their related social media discussion on a tablet computer. The attentional costs of such multitasking may vary depending on the ebb and flow of the social media channel, such as its emotional contents. In the present study, we tested the hypothesis that negative social media messages would draw more attention than similar positive messages. Specifically, news broadcasts were presented in isolation and with simultaneous positive or negative Twitter messages on a tablet to 38 participants in a controlled experiment. Recognition memory, gaze tracking, cardiac responses, and self-reports were used as attentional indices. The presence of any tweets on the tablet decreased attention to the news broadcasts. As expected, negative tweets drew longer viewing times and elicited more attention to themselves than positive tweets. Negative tweets did not, however, decrease attention to the news broadcasts. Taken together, the present results demonstrate a negativity bias exists for social media messages in media multitasking; however, this effect does not amplify the overall detrimental effects of media multitasking.

Negativity Bias in Media Multitasking: The Effects of Negative Social Media Messages on Attention to Television News Broadcasts

PubMed Central

Kätsyri, Jari; Kinnunen, Teemu; Kusumoto, Kenta; Oittinen, Pirkko; Ravaja, Niklas

2016-01-01

Television viewers’ attention is increasingly more often divided between television and “second screens”, for example when viewing television broadcasts and following their related social media discussion on a tablet computer. The attentional costs of such multitasking may vary depending on the ebb and flow of the social media channel, such as its emotional contents. In the present study, we tested the hypothesis that negative social media messages would draw more attention than similar positive messages. Specifically, news broadcasts were presented in isolation and with simultaneous positive or negative Twitter messages on a tablet to 38 participants in a controlled experiment. Recognition memory, gaze tracking, cardiac responses, and self-reports were used as attentional indices. The presence of any tweets on the tablet decreased attention to the news broadcasts. As expected, negative tweets drew longer viewing times and elicited more attention to themselves than positive tweets. Negative tweets did not, however, decrease attention to the news broadcasts. Taken together, the present results demonstrate a negativity bias exists for social media messages in media multitasking; however, this effect does not amplify the overall detrimental effects of media multitasking. PMID:27144385

Trait emotional intelligence and mental distress: the mediating role of positive and negative affect.

PubMed

Kong, Feng; Zhao, Jingjing; You, Xuqun

2012-01-01

Over the past decade, emotional intelligence (EI) has received much attention in the literature. Previous studies indicated that higher trait or ability EI was associated with greater mental distress. The present study focused on mediating effects of positive and negative affect on the association between trait EI and mental distress in a sample of Chinese adults. The participants were 726 Chinese adults (384 females) with an age range of 18-60 years. Data were collected by using the Wong Law Emotional Intelligence Scale, the Positive Affect and Negative Affect Scale, and the General Health Questionnaire. Hierarchical regression analysis showed that EI was a significant predictor of positive affect, negative affect and mental distress. Further mediation analysis showed that positive and negative affect acted as partial mediators of the relationship between EI and mental distress. Furthermore, effect contrasts showed that there was no significant difference between the specific indirect effects through positive affect and through negative affect. This result indicated that positive affect and negative affect played an equally important function in the association between EI and distress. The significance and limitations of the results are discussed.

Assessing the Personal Negative Impacts of Hooking Up Experienced by College Students: Gender Differences and Mental Health.

PubMed

Napper, Lucy E; Montes, Kevin S; Kenney, Shannon R; LaBrie, Joseph W

2016-09-01

Hooking up is a normative behavior among college students that is associated with a range of positive and negative consequences. While previous research has primarily focused on women's negative experiences of hooking up, the current study explored the relationships among hooking up behaviors, psychological distress, and a broad range of negative effects of hooking up in both male and female college students. Using a multisite sample of college students, we developed the 14-item Negative Impact of Hookups Inventory (NIHI) to assess negative health outcomes, emotional responses, and social consequences associated with hooking up. Unprotected sex and having more hookup partners were associated with greater negative experiences of hooking up. Contrary to expectations, there were no gender differences in the total number of negative hookup effects, although men reported more frequent hookups. In addition, negative impacts of hooking up were positively associated with psychological distress regardless of gender. The NIHI may offer a useful tool to assess the negative impacts of hooking up. Understanding students' hookup experiences is an important step toward developing targeted health interventions related to hooking up behavior in young adult populations.

PERCEIVED RACISM AND NEGATIVE AFFECT: ANALYSES OF TRAIT AND STATE MEASURES OF AFFECT IN A COMMUNITY SAMPLE

PubMed Central

BRONDOLO, ELIZABETH; BRADY, NISHA; THOMPSON, SHOLA; TOBIN, JONATHAN N.; CASSELLS, ANDREA; SWEENEY, MONICA; MCFARLANE, DELANO; CONTRADA, RICHARD J.

2008-01-01

Racism is a significant psychosocial stressor that is hypothesized to have negative psychological and physical health consequences. The Reserve Capacity Model (Gallo & Matthews, 2003) suggests that low socioeconomic status may influence health through its effects on negative affect. We extend this model to study the effects of racism, examining the association of lifetime perceived racism to trait and daily negative affect. A multiethnic sample of 362 American–born Black and Latino adults completed the Perceived Ethnic Discrimination Questionnaire–Community Version (PEDQ–CV). Trait negative affect was assessed with the Positive and Negative Affect Schedule (PANAS), and state negative affect was measured using ecological momentary assessments (EMA), in the form of an electronic diary. Analyses revealed a significant relationship of lifetime perceived racism to both daily negative affect and trait negative affect, even when controlling for trait hostility and socioeconomic status. The relationship of perceived racism to negative affect was moderated by education, such that the relationships were strongest for those with less than a high school education. The findings support aspects of the Reserve Capacity Model and identify pathways through which perceived racism may affect health status. PMID:19079772

Good things don't come easy (to mind): explaining framing effects in judgments of truth.

PubMed

Hilbig, Benjamin E

2012-01-01

Recently, the general phenomenon of a positive-negative-asymmetry was extended to judgments of truth. That is, negatively framed statements were shown to receive substantially higher truth ratings than formally equivalent statements framed positively. However, the cognitive mechanisms underlying this effect are unknown, so far. In the current work, two potential accounts are introduced and tested against each other in three experiments: On the one hand, negative framing may induce increased elaboration and thereby persuasion. Alternatively, negative framing could yield faster retrieval or generation of evidence and thus influence subjective veracity via experiential fluency. Two experiments drawing on response latencies and one manipulating the delay between information acquisition and judgment provide support for the fluency-based account. Overall, results replicate and extend the negatively-biased framing effect in truth judgments and show that processing fluency may account for it. © 2011 Hogrefe Publishing

The Older Adult Positivity Effect in Evaluations of Trustworthiness: Emotion Regulation or Cognitive Capacity?

PubMed

Zebrowitz, Leslie A; Boshyan, Jasmine; Ward, Noreen; Gutchess, Angela; Hadjikhani, Nouchine

2017-01-01

An older adult positivity effect, i.e., the tendency for older adults to favor positive over negative stimulus information more than do younger adults, has been previously shown in attention, memory, and evaluations. This effect has been attributed to greater emotion regulation in older adults. In the case of attention and memory, this explanation has been supported by some evidence that the older adult positivity effect is most pronounced for negative stimuli, which would motivate emotion regulation, and that it is reduced by cognitive load, which would impede emotion regulation. We investigated whether greater older adult positivity in the case of evaluative responses to faces is also enhanced for negative stimuli and attenuated by cognitive load, as an emotion regulation explanation would predict. In two studies, younger and older adults rated trustworthiness of faces that varied in valence both under low and high cognitive load, with the latter manipulated by a distracting backwards counting task. In Study 1, face valence was manipulated by attractiveness (low /disfigured faces, medium, high/fashion models' faces). In Study 2, face valence was manipulated by trustworthiness (low, medium, high). Both studies revealed a significant older adult positivity effect. However, contrary to an emotion regulation account, this effect was not stronger for more negative faces, and cognitive load increased rather than decreased the rated trustworthiness of negatively valenced faces. Although inconsistent with emotion regulation, the latter effect is consistent with theory and research arguing that more cognitive resources are required to process negative stimuli, because they are more cognitively elaborated than positive ones. The finding that increased age and increased cognitive load both enhanced the positivity of trustworthy ratings suggests that the older adult positivity effect in evaluative ratings of faces may reflect age-related declines in cognitive capacity rather than increases in the regulation of negative emotions.

Nocebo phenomena in medicine: their relevance in everyday clinical practice.

PubMed

Häuser, Winfried; Hansen, Ernil; Enck, Paul

2012-06-01

Nocebo phenomena are common in clinical practice and have recently become a popular topic of research and discussion among basic scientists, clinicians, and ethicists. We selectively searched the PubMed database for articles published up to December 2011 that contained the key words "nocebo" or "nocebo effect." By definition, a nocebo effect is the induction of a symptom perceived as negative by sham treatment and/or by the suggestion of negative expectations. A nocebo response is a negative symptom induced by the patient's own negative expectations and/or by negative suggestions from clinical staff in the absence of any treatment. The underlying mechanisms include learning by Pavlovian conditioning and reaction to expectations induced by verbal information or suggestion. Nocebo responses may come about through unintentional negative suggestion on the part of physicians and nurses. Information about possible complications and negative expectations on the patient's part increases the likelihood of adverse effects. Adverse events under treatment with medications sometimes come about by a nocebo effect. Physicians face an ethical dilemma, as they are required not just to inform patients of the potential complications of treatment, but also to minimize the likelihood of these complications, i.e., to avoid inducing them through the potential nocebo effect of thorough patient information. Possible ways out of the dilemma include emphasizing the fact that the proposed treatment is usually well tolerated, or else getting the patient's permission to inform less than fully about its possible side effects. Communication training in medical school, residency training, and continuing medical education would be desirable so that physicians can better exploit the power of words to patients' benefit, rather than their detriment.

Cosmic Rays and Clouds, 1. Formation of Lead Mesoatoms In Neutron Monitor By Soft Negative Muons and Expected Atmospheric Electric Field Effect In The Cosmic Ray Neutron Component

NASA Astrophysics Data System (ADS)

Dorman, L. I.; Dorman, I. V.

We extend our model (Dorman and Dorman, 1995) of cosmic ray atmospheric electric field effect on the case of neutron monitor. We take into account that about 0.07 of neu- tron monitor counting rate caused by negative soft muons captured by lead nucleons and formed mesoatoms with generation of several MeV energy neutrons from lead. In this case the neutron monitor or neutron supermonitor works as analyzer which de- tects muons of only one, negative sign. It is very important because the atmospheric electric field effect have opposite signs for positive and negative muons that main part of this effect in the muon telescope or in ionization chamber is compensated and we can observe only small part of total effect of one sign muons. On the basis of our gen- eral theory of cosmic ray meteorological effects with taking into account of negative soft muon acceleration and deceleration in the Earth atmosphere (in dependence of di- rection and intensity of electric field) we discuss the possibility of existing this effect in cosmic ray neutron component and made some rough estimations. REFERENCES: Dorman L.I. and Dorman I.V., 1995. "Cosmic-ray atmospheric electric field effects". Canadian J. of Physics, Vol. 73, pp. 440-443.

Negative refraction angular characterization in one-dimensional photonic crystals.

PubMed

Lugo, Jesus Eduardo; Doti, Rafael; Faubert, Jocelyn

2011-04-06

Photonic crystals are artificial structures that have periodic dielectric components with different refractive indices. Under certain conditions, they abnormally refract the light, a phenomenon called negative refraction. Here we experimentally characterize negative refraction in a one dimensional photonic crystal structure; near the low frequency edge of the fourth photonic bandgap. We compare the experimental results with current theory and a theory based on the group velocity developed here. We also analytically derived the negative refraction correctness condition that gives the angular region where negative refraction occurs. By using standard photonic techniques we experimentally determined the relationship between incidence and negative refraction angles and found the negative refraction range by applying the correctness condition. In order to compare both theories with experimental results an output refraction correction was utilized. The correction uses Snell's law and an effective refractive index based on two effective dielectric constants. We found good agreement between experiment and both theories in the negative refraction zone. Since both theories and the experimental observations agreed well in the negative refraction region, we can use both negative refraction theories plus the output correction to predict negative refraction angles. This can be very useful from a practical point of view for space filtering applications such as a photonic demultiplexer or for sensing applications.

Negative Refraction Angular Characterization in One-Dimensional Photonic Crystals

PubMed Central

Lugo, Jesus Eduardo; Doti, Rafael; Faubert, Jocelyn

2011-01-01

Background Photonic crystals are artificial structures that have periodic dielectric components with different refractive indices. Under certain conditions, they abnormally refract the light, a phenomenon called negative refraction. Here we experimentally characterize negative refraction in a one dimensional photonic crystal structure; near the low frequency edge of the fourth photonic bandgap. We compare the experimental results with current theory and a theory based on the group velocity developed here. We also analytically derived the negative refraction correctness condition that gives the angular region where negative refraction occurs. Methodology/Principal Findings By using standard photonic techniques we experimentally determined the relationship between incidence and negative refraction angles and found the negative refraction range by applying the correctness condition. In order to compare both theories with experimental results an output refraction correction was utilized. The correction uses Snell's law and an effective refractive index based on two effective dielectric constants. We found good agreement between experiment and both theories in the negative refraction zone. Conclusions/Significance Since both theories and the experimental observations agreed well in the negative refraction region, we can use both negative refraction theories plus the output correction to predict negative refraction angles. This can be very useful from a practical point of view for space filtering applications such as a photonic demultiplexer or for sensing applications. PMID:21494332

Role-modeling and medical error disclosure: a national survey of trainees.

PubMed

Martinez, William; Hickson, Gerald B; Miller, Bonnie M; Doukas, David J; Buckley, John D; Song, John; Sehgal, Niraj L; Deitz, Jennifer; Braddock, Clarence H; Lehmann, Lisa Soleymani

2014-03-01

To measure trainees' exposure to negative and positive role-modeling for responding to medical errors and to examine the association between that exposure and trainees' attitudes and behaviors regarding error disclosure. Between May 2011 and June 2012, 435 residents at two large academic medical centers and 1,187 medical students from seven U.S. medical schools received anonymous, electronic questionnaires. The questionnaire asked respondents about (1) experiences with errors, (2) training for responding to errors, (3) behaviors related to error disclosure, (4) exposure to role-modeling for responding to errors, and (5) attitudes regarding disclosure. Using multivariate regression, the authors analyzed whether frequency of exposure to negative and positive role-modeling independently predicted two primary outcomes: (1) attitudes regarding disclosure and (2) nontransparent behavior in response to a harmful error. The response rate was 55% (884/1,622). Training on how to respond to errors had the largest independent, positive effect on attitudes (standardized effect estimate, 0.32, P < .001); negative role-modeling had the largest independent, negative effect (standardized effect estimate, -0.26, P < .001). Positive role-modeling had a positive effect on attitudes (standardized effect estimate, 0.26, P < .001). Exposure to negative role-modeling was independently associated with an increased likelihood of trainees' nontransparent behavior in response to an error (OR 1.37, 95% CI 1.15-1.64; P < .001). Exposure to role-modeling predicts trainees' attitudes and behavior regarding the disclosure of harmful errors. Negative role models may be a significant impediment to disclosure among trainees.

With a little help from my assistant: buffering the negative effects of emotional dissonance on dentist performance.

PubMed

Rodríguez-Sánchez, Alma M; Hakanen, Jari J; Perhoniemi, Riku; Salanova, Marisa

2013-10-01

In this study, we hypothesized that dentist' interpersonal resources (good cooperation with one's assistant) together with their personal resources (optimism) buffer the negative effects of emotional dissonance (a demand that occurs when there is a difference between felt and displayed emotions) on job performance (in-role and extra-role performance) over time. We carried out Hierarchical Regression Modeling on a sample of 1954 Finnish dentists who participated in a two-wave 4-year longitudinal study. Results showed that good cooperation with dental assistants buffered the negative effects of emotional dissonance on both in-role and extra-role performance among the dentists in the long term. However, unexpectedly, dentists' high optimism did not buffer their in-role nor extra-role performance over time under conditions of experiencing high emotional dissonance. We conclude that interpersonal job resources such as good cooperation with one's colleagues may buffer the negative effect of emotional dissonance on dentists' job performance even in the long term, whereas the role of personal resources (e.g., optimism) may be less important for maintaining high job performance under conditions of emotional dissonance. The study novelties include the test of the negative effects of emotional dissonance on long-term performance in dentistry and the identification of the job rather than personal resources as the buffers against the negative effects of emotional dissonance on long-term performance. © 2013 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Negative cancer stereotypes and disease-specific self-concept in head and neck cancer.

PubMed

Wong, Janice C; Payne, Ada Y M; Mah, Kenneth; Lebel, Sophie; Lee, Ruth N F; Irish, Jonathan; Rodin, Gary; Devins, Gerald M

2013-05-01

Life-threatening diseases, such as head and neck cancer (HNCa), can stimulate the emergence of a new disease-specific self-concept. We hypothesized that (i) negative cancer-stereotypes invoke distancing, which inhibits the adoption of a disease-specific self-concept and (ii) patient characteristics, disease and treatment factors, and cancer-related stressors moderate the phenomenon. Head and neck cancer outpatients (N = 522) completed a semantic-differential measure of disease-specific self-concept (perceived similarity to the 'cancer patient') and other self-report measures in structured interviews. Negative cancer-stereotypes were represented by the number of semantic-differential dimensions (0-3) along which respondents evaluated the stereotypic 'cancer patient' negatively (i.e., negative valence). We tested the two-way interactions between negative valence and hypothesized moderator variables. We observed significant negative valence × moderator interactions for the following: (i) patient characteristics (education, employment, social networks); (ii) disease and treatment factors (cancer-symptom burden); and (iii) cancer-related stressors (uncertainty, lack of information, and existential threats). Negative cancer stereotypes were consistently associated with distancing of self from the stereotypic 'cancer patient,' but the effect varied across moderator variables. All significant moderators (except employment and social networks) were associated with increasing perceived similarity to the 'cancer patient' when respondents maintained negative stereotypes; perceived similarity decreased when people were employed or had extensive social networks. Moderator effects were less pronounced when respondents did not endorse negative cancer stereotypes. When they hold negative stereotypes, people with HNCa distance themselves from a 'cancer patient' identity to preserve self-esteem or social status, but exposure to cancer-related stressors and adaptive demands may attenuate these effects. Copyright © 2012 John Wiley & Sons, Ltd.

Alternative stable states and alternative endstates of community assembly through intra- and interspecific positive and negative interactions.

PubMed

Gerla, Daan J; Mooij, Wolf M

2014-09-01

Positive and negative interactions within and between species may occur simultaneously, with the net effect depending on population densities. For instance, at low densities plants may ameliorate stress, while competition for resources dominates at higher densities. Here, we propose a simple two-species model in which con- and heterospecifics have a positive effect on per capita growth rate at low densities, while negative interactions dominate at high densities. The model thus includes both Allee effects (intraspecific positive effects) and mutualism (interspecific positive effects), as well as intra- and interspecific competition. Using graphical methods we derive conditions for alternative stable states and species coexistence. We show that mutual non-invasibility (i.e. the inability of each species to invade a population of the other) is more likely when species have a strong positive effect on the own species or a strong negative effect on the other species. Mutual non-invasibility implies alternative stable states, however, there may also be alternative stable states at which species coexist. In the case of species symmetry (i.e. when species are indistinguishable), such alternative coexistence states require that if the positive effect exerted at low densities at the own species is stronger than on the other species, the negative effect at higher densities is also stronger on the own species than on the other species, or, vice versa, if the interspecific positive effects at low densities are stronger than the intraspecific effects, the negative effects at higher densities are also stronger between species than within species. However, the reachability of alternative stable states is restricted by the frequency and density at which species are introduced during community assembly, so that alternative stable states do not always represent alternative endstates of community assembly. Copyright © 2014 Elsevier Inc. All rights reserved.

Anxiety symptoms mediate the relationship between exposure to stressful negative life events and depressive symptoms: A conditional process modelling of the protective effects of resilience.

PubMed

Anyan, Frederick; Worsley, Lyn; Hjemdal, Odin

2017-10-01

Resilience has provided a useful framework that elucidates the effects of protective factors to overcome psychological adversities but studies that address the potential contingencies of resilience to protect against direct and indirect negative effects are lacking. These obvious gaps have also resulted in oversimplification of complex processes that can be clarified by moderated mediation associations. This study examines a conditional process modelling of the protective effects of resilience against indirect effects. Two separate samples were recruited in a cross-sectional survey from Australia and Norway to complete the Patient Health Questionnaire -9, Generalized Anxiety Disorder, Stressful Negative Life Events Questionnaire and the Resilience Scale for Adults. The final sample sizes were 206 (females=114; males=91; other=1) and 210 (females=155; males=55) for Australia and Norway respectively. Moderated mediation analyses were conducted across the samples. Anxiety symptoms mediated the relationship between exposure to stressful negative life events and depressive symptoms in both samples. Conditional indirect effects of exposure to stressful negative life events on depressive symptoms mediated by anxiety symptoms showed that high subgroup of resilience was associated with less effect of exposure to stressful negative life events through anxiety symptoms on depressive symptoms than the low subgroup of resilience. As a cross-sectional survey, the present study does not answer questions about causal processes despite the use of a conditional process modelling. These findings support that, resilience protective resources can protect against both direct and indirect - through other channels - psychological adversities. Copyright © 2017 Elsevier B.V. All rights reserved.