Resonating-valence-bond superconductors with fermionic projected entangled pair states

NARCIS (Netherlands)

Poilblanc, D.; Corboz, P.; Schuch, N.; Cirac, J.I.

2014-01-01

We construct a family of simple fermionic projected entangled pair states (fPEPS) on the square lattice with bond dimension D=3 which are exactly hole-doped resonating valence bond (RVB) wave functions with short-range singlet bonds. Under doping the insulating RVB spin liquid evolves immediately

Exact ground-state correlation functions of one-dimenisonal strongly correlated electron models with resonating-valence-bond ground state

International Nuclear Information System (INIS)

Yamanaka, Masanori; Honjo, Shinsuke; Kohmoto, Mahito

1996-01-01

We investigate one-dimensional strongly correlated electron models which have the resonating-valence-bond state as the exact ground state. The correlation functions are evaluated exactly using the transfer matrix method for the geometric representations of the valence-bond states. In this method, we only treat matrices with small dimensions. This enables us to give analytical results. It is shown that the correlation functions decay exponentially with distance. The result suggests that there is a finite excitation gap, and that the ground state is insulating. Since the corresponding noninteracting systems may be insulating or metallic, we can say that the gap originates from strong correlation. The persistent currents of the present models are also investigated and found to be exactly vanishing

The effects of valence-based and discrete emotional states on aesthetic response.

Science.gov (United States)

Cheng, Yin-Hui

2013-01-01

There is increasing recognition that consumer aesthetics--the responses of consumers to the aesthetic or appearance aspects of products--has become an important area of marketing in recent years. Consumer aesthetic responses to a product are a source of pleasure for the consumer. Previous research into the aesthetic responses to products has often emphasized exterior factors and visual design, but studies have seldom considered the psychological aesthetic experience of consumers, and in particular their emotional state. This study attempts to bridge this gap by examining the link between consumers' emotions and their aesthetic response to a product. Thus, the major goal of this study was to determine how valence-based and discrete emotional states influence choice. In Studies 1 and 2, positive and negative emotions were manipulated to implement two different induction techniques and explore the effect of emotions on participants' choices in two separate experiments. The results of both experiments confirmed the predictions, indicating that aesthetic responses and purchase intention are functions of emotional valence, such that both are stronger for people in a positive emotional state than for those in a negative emotional state. Study 2 also used a neutral affective state to establish the robustness of this observed effect of incidental affect. The results of Study 3 demonstrate that aesthetic response and purchase intention are not only a function of affect valence, but also are affected by the certainty appraisal associated with specific affective states. This research, therefore, contributes to the literature by offering empirical evidence that incidental affect is a determinant of aesthetic response.

Yb valence state in Yb{sub 5}Rh{sub 4}Ge{sub 10}

Energy Technology Data Exchange (ETDEWEB)

Sato, Hitoshi; Arita, Masashi; Shimada, Kenya; Namatame, Hirofumi; Taniguchi, Masaki [Hiroshima Synchrotron Radiation Center, Hiroshima University, Higashi-Hiroshima (Japan); Utsumi, Yuki [Synchrotron SOLEIL, L' Orme des Merisiers, Gif-sur-Yvette (France); Katoh, Kenichi [Department of Applied Physics, National Defense Academy, Yokosuka (Japan); Mimura, Kojiro [Graduate School of Engineering, Osaka Prefecture University, Sakai (Japan); Ueda, Shigenori [Synchrotron X-ray Station at SPring-8, National Institute for Materials Science, Hyogo (Japan); Quantum Beam Unit, National Institute for Materials Science, Tsukuba (Japan); Yamaoka, Hitoshi [RIKEN SPring-8 Center, Hyogo (Japan); Rousuli, Awabaikeli [Graduate School of Science, Hiroshima University, Higashi-Hiroshima (Japan); Umeo, Kazunori [NBARD, Hiroshima University, Higashi-Hiroshima (Japan)

2017-06-15

Temperature- and pressure-dependent Yb valence state in Yb{sub 5}Rh{sub 4}Ge{sub 10} has been investigated by means of Yb 3d hard X-ray photoemission spectroscopy (HAXPES) and Yb L{sub 3} absorption spectroscopy (XAS). The mean Yb valence derived from the Yb 3d HAXPES is estimated to be ∝2.78 at 300 K and decreases to ∝2.74 at 20 K. On the other hand, the Yb valence deduced from the Yb L{sub 3} XAS at 300 K is almost constant with ∝2.81 in the pressure range between 9.2 and 34.7 GPa. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Valence skipping driven superconductivity and charge Kondo effect

International Nuclear Information System (INIS)

Yanagisawa, Takashi; Hase, Izumi

2013-01-01

Highlights: •Valence skipping in metallic compounds can give rise to an unconventional superconductivity. •Several elements in the periodic table show valence skipping (or valence missing), for example, Bi forms the compounds in valence states +3 and +5. •The doping of valence skipping elements will induce superconductivity and this will lead to a possibility of high temperature superconductivity. •We consider the Wolf model with negative-U impurities, and show a phase diagram including superconducting phase. •There is a high temperature region near the boundary. -- Abstract: Valence skipping in metallic compounds can give rise to an unconventional superconductivity. Several elements in the periodic table show valence skipping (or valence missing), for example, Bi forms the compounds in valence states +3 and +5. The doping of valence skipping elements will induce superconductivity and this will lead to a possibility of high temperature superconductivity. We consider the Wolf model with negative-U impurities, and show a phase diagram including superconducting phase. The superconducting state is changed into a metallic state with a local singlet as the attractive interaction |U| increases. There is a high temperature region near the boundary

Ground state and elementary excitations of a model valence-fluctuation system

International Nuclear Information System (INIS)

Brandow, B.H.

1979-01-01

The nature of the valence fluctuation problem is described, and motivations are given for an Anderson-lattice model Hamiltonian. A simple trial wave function is posed for the ground state, and the variational problem is solved. This demonstrates clearly that there is no Kondo-like divergence; the present concentrated Kondo problem is thus more simple mathematically than the sngle-impurity problem. Elementary excitations are studies by the Green's function techniques of Zubarev and Hubbard. Quenching of local moments and a large specific heat are found at low temperatures. The quasi-particle spectrum exhibits a gap, but epsilon/sub F/ does not lie in this gap. The insulation-like feature of SmB 6 , SmS, and TmSe at very low temperatures is explained in terms of a strongly reduced mobility for states near the gap, and reasons are given why this feature is not observed in other valence-fluctuation compounds. 73 references

The valence state of Yb metal under high pressure determined by XANES measurement up to 34.6 GPa

International Nuclear Information System (INIS)

Fuse, Akinori; Nakamoto, Go; Kurisu, Makio; Ishimatsu, Naoki; Tanida, Hajime

2004-01-01

The purpose of this study was to accurately determine the valency of Yb at high pressure and room temperature and to clarify the relation between the valence state and the crystal structure of Yb metal. L III -edge X-ray absorption near-edge structure (XANES) spectra were measured to determine the valence state of Yb metal in the pressure range from 0 to 34.6 GPa at room temperature, using a diamond anvil cell (DAC) and synchrotron radiation at SPring-8. In the fcc phase, Yb metal exhibits mixed valence (the mean valence ν-bar >2.1). At the fcc-to-bcc phase transition, a 0.1 jump is found in ν-bar. In the bcc phase, ν-bar(P) is an increasing function of pressure with downward curvature, reaching only 2.55 at 26 GPa. The ν-bar is only 2.65 in the hcp phase at 34.6 GPa. A tendency for saturation in ν-bar(P) to values smaller than 3.0 is found

A complex of cardiac cytochrome c1 and cytochrome c.

Science.gov (United States)

Chiang, Y L; Kaminsky, L S; King, T E

1976-01-10

The interactions of cytochrome c1 and cytochrome c from bovine cardiac mitochondria were investigated. Cytochrome c1 and cytochrome c formed a 1:1 molecular complex in aqueous solutions of low ionic strength. The complex was stable to Sephadex G-75 chromatography. The formation and stability of the complex were independent of the oxidation state of the cytochrome components as far as those reactions studied were concerned. The complex was dissociated in solutions of ionic strength higher than 0.07 or pH exceeding 10 and only partially dissociated in 8 M urea. No complexation occurred when cytochrome c was acetylated on 64% of its lysine residues or photooxidized on its 2 methionine residues. Complexes with molecular ratios of less than 1:1 (i.e. more cytochrome c) were obtained when polymerized cytochrome c, or cytochrome c with all lysine residues guanidinated, or a "1-65 heme peptide" from cyanogen bromide cleavage of cytochrome c was used. These results were interpreted to imply that the complex was predominantly maintained by ionic interactions probably involving some of the lysine residues of cytochrome c but with major stabilization dependent on the native conformations of both cytochromes. The reduced complex was autooxidizable with biphasic kinetics with first order rate constants of 6 X 10(-5) and 5 X U0(-5) s-1 but did not react with carbon monoxide. The complex reacted with cyanide and was reduced by ascorbate at about 32% and 40% respectively, of the rates of reaction with cytochrome c alone. The complex was less photoreducible than cytochrome c1 alone. The complex exhibited remarkably different circular dichroic behavior from that of the summation of cytochrome c1 plus cytochrome c. We concluded that when cytochromes c1 and c interacted they underwent dramatic conformational changes resulting in weakening of their heme crevices. All results available would indicate that in the complex cytochrome c1 was bound at the entrance to the heme crevice of

Conjugation of cytochrome c with hydrogen titanate nanotubes: novel conformational state with implications for apoptosis

Energy Technology Data Exchange (ETDEWEB)

Ray, Moumita; Mazumdar, Shyamalava [Department of Chemical Sciences, Tata Institute of Fundamental Research, Homi Bhabha Road, Mumbai 400005 (India); Chatterjee, Sriparna; Das, Tanmay; Bhattacharyya, Somnath; Ayyub, Pushan, E-mail: somnath@tifr.res.in, E-mail: pushan@tifr.res.in, E-mail: shyamal@tifr.res.in [Department of Condensed Matter Physics and Materials Science, Tata Institute of Fundamental Research, Homi Bhabha Road, Mumbai 400005 (India)

2011-10-14

We show that hydrogen titanate (H{sub 2}Ti{sub 3}O{sub 7}) nanotubes form strongly associated reversible nano-bio-conjugates with the vital respiratory protein, cytochrome c. Resonance Raman spectroscopy along with direct electrochemical studies indicate that in this nano-bio-conjugate, cytochrome c exists in an equilibrium of two conformational states with distinctly different formal redox potentials and coordination geometries of the heme center. The nanotube-conjugated cytochrome c also showed enhanced peroxidase activity similar to the membrane-bound protein that is believed to be an apoptosis initiator. This suggests that such a nanotube-cytochrome c conjugate may be a good candidate for cancer therapy applications.

Equation of states and phonons at high pressure of intermediate valence compound TmTe

International Nuclear Information System (INIS)

Jha, Prafulla K.; Sanyal, Sankar P.

1997-01-01

The study of equation of states and pressure dependence of the phonon frequencies of the compound TmTe have been performed by using a simple interatomic potential approach in the frame work of rigid ion model. The compressibility study confirms that below 2 GPa the valence of the Tm is 2+ while there is a valence transition from Tm 2+ to Tm 3+ above 2 GPa. The phonon frequencies of TmTe increases as pressure is increased. (author)

Magnetic excitations in intermediate valence semiconductors with singlet ground state

International Nuclear Information System (INIS)

Kikoin, K.A.; Mishchenko, A.S.

1994-01-01

The explanation of the origin inelastic peaks in magnetic neutron scattering spectra of the mixed-valent semiconductor SmB 6 is proposed. It is shown that the excitonic theory of intermediate valence state not only gives the value of the peak frequency but also explains the unusual angular dependence of intensity of inelastic magnetic scattering and describes the dispersion of magnetic excitations in good agreement with experiment

Entanglement of the valence-bond-solid state on an arbitrary graph

International Nuclear Information System (INIS)

Xu Ying; Korepin, Vladimir E

2008-01-01

The Affleck-Kennedy-Lieb-Tasaki (AKLT) spin interacting model can be defined on an arbitrary graph. We explain the construction of the AKLT Hamiltonian. Given certain conditions, the ground state is unique and known as the valence-bond-solid (VBS) state. It can be used in measurement-based quantum computation as a resource state instead of the cluster state. We study the VBS ground state on an arbitrary connected graph. The graph is cut into two disconnected parts: the block and the environment. We study the entanglement between these two parts and prove that many eigenvalues of the density matrix of the block are zero. We describe a subspace of eigenvectors of the density matrix corresponding to non-zero eigenvalues. The subspace is the degenerate ground states of some Hamiltonian which we call the block Hamiltonian

Unifying Exchange Sensitivity in Transition-Metal Spin-State Ordering and Catalysis through Bond Valence Metrics.

Science.gov (United States)

Gani, Terry Z H; Kulik, Heather J

2017-11-14

Accurate predictions of spin-state ordering, reaction energetics, and barrier heights are critical for the computational discovery of open-shell transition-metal (TM) catalysts. Semilocal approximations in density functional theory, such as the generalized gradient approximation (GGA), suffer from delocalization error that causes them to overstabilize strongly bonded states. Descriptions of energetics and bonding are often improved by introducing a fraction of exact exchange (e.g., erroneous low-spin GGA ground states are instead correctly predicted as high-spin with a hybrid functional). The degree of spin-splitting sensitivity to exchange can be understood based on the chemical composition of the complex, but the effect of exchange on reaction energetics within a single spin state is less well-established. Across a number of model iron complexes, we observe strong exchange sensitivities of reaction barriers and energies that are of the same magnitude as those for spin splitting energies. We rationalize trends in both reaction and spin energetics by introducing a measure of delocalization, the bond valence of the metal-ligand bonds in each complex. The bond valence thus represents a simple-to-compute property that unifies understanding of exchange sensitivity for catalytic properties and spin-state ordering in TM complexes. Close agreement of the resulting per-metal-organic-bond sensitivity estimates, together with failure of alternative descriptors demonstrates the utility of the bond valence as a robust descriptor of how differences in metal-ligand delocalization produce differing relative energetics with exchange tuning. Our unified description explains the overall effect of exact exchange tuning on the paradigmatic two-state FeO + /CH 4 reaction that combines challenges of spin-state and reactivity predictions. This new descriptor-sensitivity relationship provides a path to quantifying how predictions in transition-metal complex screening are sensitive to the

Micro-Valences: Affective valence in neutral everyday objects

Directory of Open Access Journals (Sweden)

Sophie eLebrecht

2012-04-01

Full Text Available Affective valence influences both our cognition and our perception of the world. Indeed, the speed and quality with which we recognize objects in a visual scene can vary dramatically depending on its affective content. However, affective processing of visual objects has been typically studied using only stimuli with strong affective valences (e.g., guns or roses. Here we explore whether affective valence must be strong or obvious to exert an effect on our perception. We conclude that the majority of objects carry some affective valence (micro-valences and, thus, nominally neutral objects are not really neutral. Functionally, the perception of valence in everyday objects facilitates perceptually-driven choice behavior, decision-making, and affective responses.

Stabilization of neptunium valence states in nitric media for spent nuclear fuel reprocessing

International Nuclear Information System (INIS)

Feldhaus, P.

1996-12-01

A possibility of standarizing the extraction-behavior of Neptunium during the reprocessing of spent nuclear fuel corresponding to PUREX-Process was investigated. The aim of the work was a qualitative dirigation of the Transuraniumelement (TRUE) into the raffinat of the first extraction cycle by a complete redoxconversion of the Neptunium valence states to unextractable Np(V). In the beginning the theoretical and experimental research focussed on the redoxchemistry of the actinide during the fuel dissolution and the feed preparation. Thereby the nitrous acid, which is produced by a radiological, photochemical and reductive degradation of the nitric acid, revealed an ambivalent influence on the Neptunium valences. By a short-term increase in HNO 2 -concentration the Np(V)-fraction could be obviously risen. The use of some stabilizing reagents inhibited a later reoxidation to Np(VI) also catalyzed by nitrous acid. The urea used for this purpose also led to a further increase in the obtained conversion rates due to a Np(VI)-reduction. The analysis of the valence distribution was performed by an extraction method. This had been compared to chromatographic separation in some preliminary investigations and had turned out to be comparably reliable and easily manageable. (orig.) [de

Theory of two-photon absorption by exciton states in cubic semiconductors with degenerate valence bands

International Nuclear Information System (INIS)

Nguyen Ai Viet; Nguyen Toan Thang.

1987-06-01

The coefficient of the absorption of two polarized photons is calculated for direct band gap semiconductors with degenerate valence bands. Wannier-Mott exciton states are included in both the intermediate and final states. Numerical calculations are performed for ZnSe and are compared with Sondergeld's experimental and theoretical results. (author). 11 refs, 2 tabs

A study of the valence shell electronic states of s-triazine by photoabsorption spectroscopy and ab initio calculations

DEFF Research Database (Denmark)

Holland, D.M.P.; Shaw, D.A.; Stener, Mauro

2016-01-01

absorption bands due to excitation from the 1e00 or 6e0 orbitals. The interpretation of the experimental spectrum has been guided by transition energies and oscillator strengths, for Rydberg and valence states, calculated with the time-dependent version of density functional theory and with the coupled...... cluster linear response approach. The theoretical studies indicate that Rydberg/Rydberg and Rydberg/valence mixing is important....

Interatomic decay of inner-valence ionized states in ArXe clusters: Relativistic approach

International Nuclear Information System (INIS)

Fasshauer, Elke; Pernpointner, Markus; Gokhberg, Kirill

2013-01-01

In this work we investigate interatomic electronic decay processes taking place in mixed argon-xenon clusters upon the inner-valence ionization of an argon center. We demonstrate that both interatomic Coulombic decay and electron-transfer mediated decay (ETMD) are important in larger rare gas clusters as opposed to dimers. Calculated secondary electron spectra are shown to depend strongly on the spin-orbit coupling in the final states of the decay as well as the presence of polarizable environment. It follows from our calculations that ETMD is a pure interface process taking place between the argon-xenon layers. The interplay of all these effects is investigated in order to arrive at a suitable physical model for the decay of inner-valence vacancies taking place in mixed ArXe clusters.

Levels of valence

Directory of Open Access Journals (Sweden)

Vera eShuman

2013-05-01

Full Text Available The distinction between the positive and the negative is fundamental in our emotional life. In appraisal theories, in particular in the component process model of emotion (Scherer, 1984, 2010, qualitatively different types of valence are proposed based on appraisals of (unpleasantness, goal obstructiveness/conduciveness, low or high power, self- (incongruence, and moral badness/goodness. This multifaceted conceptualization of valence is highly compatible with the frequent observation of mixed feelings in real life. However, it seems to contradict the one-dimensional conceptualization of valence often encountered in psychological theories, and the notion of valence as a common currency used to explain choice behavior. Here, we propose a framework to integrate the seemingly disparate conceptualizations of multifaceted valence and one-dimensional valence by suggesting that valence should be conceived at different levels, micro and macro. Micro-valences correspond to qualitatively different types of evaluations, potentially resulting in mixed feelings, whereas one-dimensional macro-valence corresponds to an integrative common currency to compare alternatives for choices. We propose that conceptualizing levels of valence may focus research attention on the mechanisms that relate valence at one level (micro to valence at another level (macro, leading to new hypotheses and addressing various concerns that have been raised about the valence concept, such as the valence-emotion relation.

Valence photoelectron spectrum of KBr: Effects of electron correlation

International Nuclear Information System (INIS)

Calo, A.; Huttula, M.; Patanen, M.; Aksela, H.; Aksela, S.

2008-01-01

The valence photoelectron spectrum has been measured for molecular KBr. Experimental energies of the main and satellite structures have been compared with the results of ab initio calculations based on molecular orbital theory including configuration and multiconfiguration interaction approaches. Comparison between the experimental KBr spectrum and previously reported Kr valence photoelectron spectrum has also been performed in order to find out if electron correlation is of the same importance in the valence ionized state of KBr as in the corresponding state of Kr

Valence, arousal and cognitive control: A voluntary task switching study

Directory of Open Access Journals (Sweden)

Jelle eDemanet

2011-11-01

Full Text Available The present study focused on the interplay between arousal, valence and cognitive control. To this end, we investigated how arousal and valence associated with affective stimuli influenced cognitive flexibility when switching between tasks voluntarily. Three hypotheses were tested. First, a valence hypothesis that states that the positive valence of affective stimuli will facilitate both global and task-switching performance because of increased cognitive flexibility. Second, an arousal hypothesis that states that arousal, and not valence, will specifically impair task-switching performance by strengthening the previously executed task-set. Third, an attention hypothesis that states that both cognitive and emotional control ask for limited attentional resources, and predicts that arousal will impair both global and task-switching performance. The results showed that arousal affected task-switching but not global performance, possibly by phasic modulations of the noradrenergic system that reinforces the previously executed task. In addition, positive valence only affected global performance but not task-switching performance, possibly by phasic modulations of dopamine that stimulates the general ability to perform in a multitasking environment.

Levels of Valence

Science.gov (United States)

Shuman, Vera; Sander, David; Scherer, Klaus R.

2013-01-01

The distinction between the positive and the negative is fundamental in our emotional life. In appraisal theories, in particular in the component process model of emotion (Scherer, 1984, 2010), qualitatively different types of valence are proposed based on appraisals of (un)pleasantness, goal obstructiveness/conduciveness, low or high power, self-(in)congruence, and moral badness/goodness. This multifaceted conceptualization of valence is highly compatible with the frequent observation of mixed feelings in real life. However, it seems to contradict the one-dimensional conceptualization of valence often encountered in psychological theories, and the notion of valence as a common currency used to explain choice behavior. Here, we propose a framework to integrate the seemingly disparate conceptualizations of multifaceted valence and one-dimensional valence by suggesting that valence should be conceived at different levels, micro and macro. Micro-valences correspond to qualitatively different types of evaluations, potentially resulting in mixed feelings, whereas one-dimensional macro-valence corresponds to an integrative “common currency” to compare alternatives for choices. We propose that conceptualizing levels of valence may focus research attention on the mechanisms that relate valence at one level (micro) to valence at another level (macro), leading to new hypotheses, and addressing various concerns that have been raised about the valence concept, such as the valence-emotion relation. PMID:23717292

Mapping of redox state of mitochondrial cytochromes in live cardiomyocytes using Raman microspectroscopy

DEFF Research Database (Denmark)

Brazhe, Nadezda A; Treiman, Marek; Brazhe, Alexey R

2012-01-01

This paper presents a nonivasive approach to study redox state of reduced cytochromes [Formula: see text], [Formula: see text] and [Formula: see text] of complexes II and III in mitochondria of live cardiomyocytes by means of Raman microspectroscopy. For the first time with the proposed approach ...

Analysis of Ti valence states in resistive switching regions of a rutile TiO2‑ x four-terminal memristive device

Science.gov (United States)

Yamaguchi, Kengo; Takeuchi, Shotaro; Tohei, Tetsuya; Ikarashi, Nobuyuki; Sakai, Akira

2018-06-01

We have performed Ti valence state analysis of our four-terminal rutile TiO2‑ x single-crystal memristors using scanning transmission electron microscopy–electron energy loss spectroscopy (STEM–EELS). Analysis of Ti-L2,3 edge EELS spectra revealed that the electrocolored region formed by the application of voltage includes a valence state reflecting highly reduced TiO2‑ x due to the accumulation of oxygen vacancies. Such a valence state mainly exists within ∼50 nm from the crystal surface and extends along specific crystal directions. These electrically reduced surface layers are considered to directly contribute to the resistive switching (RS) in the four-terminal device. The present results add new insights into the microscopic mechanisms of the RS phenomena and should contribute to further development and improvements of TiO2‑ x based memristive devices.

A Combined Theoretical and Experimental View on Valence and Conduction Band Densities of States of Lead Halide Perovskites

Science.gov (United States)

Kronik, Leeor; Endres, James; Egger, David A.; Kulbak, Michael; Kerner, Ross A.; Zhao, Lianfeng; Silver, Scott H.; Hodes, Gary; Rand, Barry P.; Cahen, David; Kahn, Antoine

We present results for the valence and conduction band density of states (DOS), measured via ultraviolet and inverse photoemission spectroscopies for three lead halide perovskites. Specifically, the DOS of MAPbI3, MAPbBr3, and CsPbBr3, grown on different substrates, are compared. Theoretical DOS, calculated via hybrid density functional theory and including spin-orbit coupling, are compared to experimental data. The agreement between experiment and theory, obtained after correcting the latter for quantitative discrepancies, leads to the identification of valence and conduction band spectral features. In particular, this comparison allows for precise determination of the energy position of the band edges, namely ionization energies and electron affinities of these materials. We find an unusually low DOS at the valence band maximum (VBM) of these systems, which confirms and generalizes previous findings of strong band dispersion and low DOS at the VBM of MAPbI3. This calls for special attention when using electron spectroscopy to determine the frontier electronic states of lead halide perovskites.

Visible light photoreactivity from hybridization states between carbon nitride bandgap states and valence states in Nb and Ti oxides

Energy Technology Data Exchange (ETDEWEB)

Lee, Hosik, E-mail: hosiklee@gmail.com [School of Mechanical and Advanced Materials Engineering, Ulsan National Institute of Science and Technology (UNIST), Unist-gil 100 Eonyang-eup, Ulsan 689-798 (Korea, Republic of); Ohno, Takahisa, E-mail: OHNO.Takahisa@nims.go.jp [Global Research Center for Environment and Energy based on Nanomaterials Science (GREEN), National Institute for Material Science, 1-2-1 Sengen, Tsukuba (Japan); Computational Materials Science Unit (CMSU), National Institute for Materials Science (NIMS), Tsukuba, Ibaraki 305-0047 (Japan)

2013-03-29

Highlights: ► Origin of bandgap reduction for visible photoreactivity is suggested. ► Carbon nitride adsorption in interlayer space can induce the bandgap reduction. ► The electronic structures are studied by density functional theory calculations. - Abstract: For better efficiency as photocatalysts, N-doping for visible light reactivity has been intensively studied in Lamellar niobic and titanic solid acids (HNb{sub 3}O{sub 8}, H{sub 2}Ti{sub 4}O{sub 9}), and its microscopic structures have been debated in this decade. We calculate the layered solid acids’ structures and bandgaps. Bandgap reduction by carbon nitride adsorption in interlayer space is observed computationally. It originates from localized nitrogen states which form delocalized top-valence states by hybridizing with the host oxygen states and can contribute to photo-current.

The mechanism by which oxygen and cytochrome c increase the rate of electron transfer from cytochrome a to cytochrome a3 of cytochrome c oxidase.

Science.gov (United States)

Bickar, D; Turrens, J F; Lehninger, A L

1986-11-05

When cytochrome c oxidase is isolated from mitochondria, the purified enzyme requires both cytochrome c and O2 to achieve its maximum rate of internal electron transfer from cytochrome a to cytochrome a3. When reductants other than cytochrome c are used, the rate of internal electron transfer is very slow. In this paper we offer an explanation for the slow reduction of cytochrome a3 when reductants other than cytochrome c are used and for the apparent allosteric effects of cytochrome c and O2. Our model is based on the conventional understanding of cytochrome oxidase mechanism (i.e. electron transfer from cytochrome a/CuA to cytochrome a3/CuB), but assumes a relatively rapid two-electron transfer between cytochrome a/CuA and cytochrome a3/CuB and a thermodynamic equilibrium in the "resting" enzyme (the enzyme as isolated) which favors reduced cytochrome a and oxidized cytochrome a3. Using the kinetic constants that are known for this reaction, we find that the activating effects of O2 and cytochrome c on the rate of electron transfer from cytochrome a to cytochrome a3 conform to the predictions of the model and so provide no evidence of any allosteric effects or control of cytochrome c oxidase by O2 or cytochrome c.

Helical Propensity Affects the Conformational Properties of the Denatured State of Cytochrome c'.

Science.gov (United States)

Danielson, Travis A; Bowler, Bruce E

2018-01-23

Changing the helical propensity of a polypeptide sequence might be expected to affect the conformational properties of the denatured state of a protein. To test this hypothesis, alanines at positions 83 and 87 near the center of helix 3 of cytochrome c' from Rhodopseudomonas palustris were mutated to serine to decrease the stability of this helix. A set of 13 single histidine variants in the A83S/A87S background were prepared to permit assessment of the conformational properties of the denatured state using histidine-loop formation in 3 M guanidine hydrochloride. The data are compared with previous histidine-heme loop formation data for wild-type cytochrome c'. As expected, destabilization of helix 3 decreases the global stabilities of the histidine variants in the A83S/A87S background relative to the wild-type background. Loop stability versus loop size data yields a scaling exponent of 2.1 ± 0.2, similar to the value of 2.3 ± 0.2 obtained for wild-type cytochrome c'. However, the stabilities of all histidine-heme loops, which contain the helix 3 sequence segment, are increased in the A83S/A87S background compared to the wild-type background. Rate constants for histidine-heme loop breakage are similar for the wild-type and A83S/A87S variants. However, for histidine-heme loops that contain the helix 3 sequence segment, the rate constants for loop formation increase in the A83S/A87S background compared to the wild-type background. Thus, residual helical structure appears to stiffen the polypeptide chain slowing loop formation in the denatured state. The implications of these results for protein folding mechanisms are discussed. Copyright © 2017 Biophysical Society. Published by Elsevier Inc. All rights reserved.

ULTRASONIC NEBULIZATION AND ARSENIC VALENCE STATE CONSIDERATIONS PRIOR TO DETERMINATION VIA INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY

Science.gov (United States)

An ultrasonic nebulizer (USN) was utilized as a sample introduction device for an inductively coupled plasma mass spectrometer in an attempt to increase the sensitivity for As. The USN produced a valence state response difference for As. The As response was suppressed approximate...

Ab initio investigation on the valence and dipole-bound states of CNa - and SiNa -

Science.gov (United States)

Kalcher, Josef; Sax, Alexander F.

2000-08-01

CNa - and SiNa - have been studied by the CAS-ACPF method. The 3Σ- ground states have binding energies of 5420 and 7517 cm -1, respectively. The 5Σ- excited states are 494 and 1551 cm -1 above the respective ground states. The 1Δ , 3Π , and 1Π valence-excited states for SiNa - should be at least metastable. CNa - and SiNa - possess dipole-bound 5Σ- and 3Σ- states. Binding energies of these states in CNa - are 217 and 236 cm -1, respectively. SiNa - has two stable 5Σ- dipole-bound states, whose binding energies are 246 and 118 cm -1, respectively.

Valence configurations in 214Rn

International Nuclear Information System (INIS)

Dracoulis, G.D.; Byrne, A.P.; Stuchbery, A.E.; Bark, R.A.; Poletti, A.R.

1987-01-01

Excited states of 214 Rn, up to spins of ≅ 24 ℎ have been studied using γ-ray and electron spectroscopy following the 208 Pb( 9 Be,3n) 214 Rn reaction. The level scheme (which differs substantially from earlier work) is compared with the results of a semi-empirical shell model calculation. The availability of high-spin orbitals for the four valence protons and two valence neutrons, and the effect of the attractive proton-neutron interaction, leads to the prediction of high-spin states at an unusually low excitation energy. Experimentally, the high level density leads to difficulties in the level scheme assignments at high spin. Nevertheless, configuration assignments, supported by transition strengths deduced from the measured lifetimes (in the nanosecond region) are suggested for the main yrast states. The decay properties also suggest that configuration mixing is important. The possibility of a gradual transition to octupole deformation, implied by the decay properties of the 11 - and 10 + yrast states is also discussed. (orig.)

The effect of cerium valence states at cerium oxide nanoparticle surfaces on cell proliferation

KAUST Repository

Naganuma, Tamaki

2014-05-01

Understanding and controlling cell proliferation on biomaterial surfaces is critical for scaffold/artificial-niche design in tissue engineering. The mechanism by which underlying integrin ligates with functionalized biomaterials to induce cell proliferation is still not completely understood. In this study, poly-l-lactide (PL) scaffold surfaces were functionalized using layers of cerium oxide nanoparticles (CNPs), which have recently attracted attention for use in therapeutic application due to their catalytic ability of Ce4+ and Ce3+ sites. To isolate the influence of Ce valance states of CNPs on cell proliferation, human mesenchymal stem cells (hMSCs) and osteoblast-like cells (MG63) were cultured on the PL/CNP surfaces with dominant Ce4+ and Ce3+ regions. Despite cell type (hMSCs and MG63 cells), different surface features of Ce4+ and Ce3+ regions clearly promoted and inhibited cell spreading, migration and adhesion behavior, resulting in rapid and slow cell proliferation, respectively. Cell proliferation results of various modified CNPs with different surface charge and hydrophobicity/hydrophilicity, indicate that Ce valence states closely correlated with the specific cell morphologies and cell-material interactions that trigger cell proliferation. This finding suggests that the cell-material interactions, which influence cell proliferation, may be controlled by introduction of metal elements with different valence states onto the biomaterial surface. © 2014 Elsevier Ltd.

Micro-Valences: Affective valence in neutral everyday objects

OpenAIRE

Sophie eLebrecht; Moshe eBar; Lisa F Barrett; Michael J Tarr

2012-01-01

Affective valence influences both our cognition and our perception of the world. Indeed, the speed and quality with which we recognize objects in a visual scene can vary dramatically depending on its affective content. However, affective processing of visual objects has been typically studied using only stimuli with strong affective valences (e.g., guns or roses). Here we explore whether affective valence must be strong or obvious to exert an effect on our perception. We conclude that the maj...

Valence-delocalization of the mixed-valence oxo-centered trinuclear iron propionates [FeIII2FeIIO(C2H5CO2)6(py)3[npy; n = 0, 1.5

International Nuclear Information System (INIS)

Nakamoto, Tadahiro; Katada, Motomi; Kawata, Satoshi; Kitagawa, Susumu; Sano, Hirotoshi; Konno, Michiko

1994-01-01

Mixed-valence trinuclear iron propionates [Fe III 2 Fe II O(C 2 H 5 CO 2 ) 6 (py) 3 [npy, where n = 0, 1.5, were synthesized and the structure of the pyridine-solvated complex was determined by single-crystal X-ray diffraction. Moessbauer spectra of the solvated propionate complex showed a temperature-dependent mixed-valence state related to phase transitions, reaching an almost delocalized valence state at room temperature. On the other hand, the non-solvated propionate showed a remarkable change of the spectral shape related to a phase transition, remaining in a localized valence state at higher temperatures up to room temperature. (orig.)

Valence states of cobalt and crystal structure peculiarities of solid solution YBa2Cu3-xCoxO6+σ

International Nuclear Information System (INIS)

Voronin, V.I.; Goshchinskij, B.N.; Mitberg, Eh.B.; Leonidov, I.A.; Kozhevnikov, V.L.

2000-01-01

Crystal structure of solid solution YBa 2 Cu 3-x Co x O 6+σ , where x = 0.2, 0.4, 0.6 and 0.8, is studied by the method of powder neutron diffraction. Charge states of the cation are calculated using the interatomic distances obtained. It is shown that cobalt in Cu1 position has valency 3 + and octahedral coordination at x = 0.2 and 0.4. Increase in doping degree involves both transition of a portion of cobalt ions in the positions mentioned to the state with valence 4 + and tetrahedral coordination and partial substitution of copper in Cu2 position [ru

Moessbauer spectroscopic study on valence-detrapping and trapping of mixed-valence trinuclear iron (III, III, II) fluorine-substitute benzoate complexes

International Nuclear Information System (INIS)

Sakai, Y.; Onaka, S.; Ogiso, R.; Takayama, T.; Takahashi, M.; Nakamoto, T.

2012-01-01

Four mixed-valence trinuclear iron(III, III, II) fluorine-substituted benzoate complexes were synthesized; Fe 3 O(C 6 F 5 COO) 6 (C 5 H 5 N) 3 ·CH 2 Cl 2 (1), Fe 3 O(C 6 F 5 COO) 6 (C 5 H 5 N) 3 (2), Fe 3 O(2H-C 6 F 4 COO) 6 (C 5 H 5 N) 3 (3), and Fe 3 O(4H-C 6 F 4 COO) 6 (C 5 H 5 N) 3 (4). By means of 57 Fe-Moessbauer spectroscopy, valence-detrapping and trapping phenomena have been investigated for the four mixed-valence complexes. The valence state of three iron ions is trapped at lower temperatures while it is fully detrapped at higher temperatures for 1. Valence detrapping is not observed for 2, 3, and 4 even at room temperature, although Moessbauer spectra for 3 and 4 show a complicated temperature dependence. (author)

Excitations of one-valence-proton, one-valence-neutron nucleus {sup 210}Bi from cold-neutron capture

Energy Technology Data Exchange (ETDEWEB)

Cieplicka-Oryńczak, N. [INFN sezione di Milano, Via Celoria 16, 20133 Milano (Italy); Institute of Nuclear Physics, Polish Academy of Sciences, PL-31342 Kraków (Poland); Fornal, B.; Szpak, B. [Institute of Nuclear Physics, Polish Academy of Sciences, PL-31342 Kraków (Poland); Leoni, S.; Bottoni, S. [INFN sezione di Milano, Via Celoria 16, 20133 Milano (Italy); Università degli Studi di Milano, Via Celoria 16, 20133 Milano (Italy); Bazzacco, D. [Dipartimento di Fisica e Astronomia dell’Università, I-35131 Padova (Italy); INFN Sezione di Padova, I-35131 Padova (Italy); Blanc, A.; Jentschel, M.; Köster, U.; Mutti, P.; Soldner, T. [Institute Laue-Langevin, 6, rue Jules Horowitz, 38042 Grenoble Cedex 9 (France); Bocchi, G. [Università degli Studi di Milano, Via Celoria 16, 20133 Milano (Italy); France, G. de [GANIL, Bd. Becquerel, BP 55027, 14076 CAEN Cedex 05 (France); Simpson, G. [LPSC, Université Joseph Fourier Grenoble 1, CNRS/IN2P3, Institut National Polytechnique de Grenoble, F-38026 Grenoble Cedex (France); Ur, C. [INFN Sezione di Padova, Via F. Marzolo 8, I-35131 Padova (Italy); Urban, W. [Faculty of Physics, University of Warsaw, ul. Hoża 69, 02-681, Warszawa (Poland)

2015-10-15

The low-spin structure of one-proton, one-neutron {sup 210}Bi nucleus was investigated in cold-neutron capture reaction on {sup 209}Bi. The γ-coincidence measurements were performed with use of EXILL array consisted of 16 HPGe detectors. The experimental results were compared to shell-model calculations involving valence particles excitations. The {sup 210}Bi nucleus offers the potential to test the effective proton-neutron interactions because most of the states should arise from the proton-neutron excitations. Additionally, it was discovered that a few states should come from the couplings of valence particles to the 3{sup −} octupole vibration in {sup 208}Pb which provides also the possibility of testing the calculations involving the core excitations.

Band width and multiple-angle valence-state mapping of diamond

International Nuclear Information System (INIS)

Jimenez, I.; Terminello, L.J.; Sutherland, D.G.J.

1997-01-01

The band width may be considered the single most important parameter characterizing the electronic structure of a solid. The ratio of band width and Coulomb repulsion determines how correlated or delocalized an electron system is. Some of the most interesting solids straddle the boundary between localized and delocalized, e.g. the high-temperature superconductors. The bulk of the band calculations available today is based on local density functional (DF) theory. Even though the Kohn-Sham eigenvalues from that theory do not represent the outcome of a band-mapping experiment, they are remarkably similar to the bands mapped via photoemission. Strictly speaking, one should use an excited state calculation that takes the solid's many-body screening response to the hole created in photoemission into account. Diamond is a useful prototype semiconductor because of its low atomic number and large band width, which has made it a long-time favorite for testing band theory. Yet, the two experimental values of the band width of diamond have error bars of ±1 eV and differ by 3.2 eV. To obtain an accurate valence band width for diamond, the authors use a band-mapping method that collects momentum distributions instead of the usual energy distributions. This method has undergone extensive experimental and theoretical tests in determining the band width of lithium fluoride. An efficient, imaging photoelectron spectrometer is coupled with a state-of-the-art undulator beam line at the Advanced Light Source to allow collection of a large number of data sets. Since it takes only a few seconds to take a picture of the photoelectrons emitted into a 84 degrees cone, the authors can use photon energies as high as 350 eV where the cross section for photoemission from the valence band is already quite low, but the emitted photoelectrons behave free-electron-like. This make its much easier to locate the origin of the inter-band transitions in momentum space

Band width and multiple-angle valence-state mapping of diamond

Energy Technology Data Exchange (ETDEWEB)

Jimenez, I.; Terminello, L.J.; Sutherland, D.G.J. [Lawrence Berkeley National Lab., CA (United States)] [and others

1997-04-01

The band width may be considered the single most important parameter characterizing the electronic structure of a solid. The ratio of band width and Coulomb repulsion determines how correlated or delocalized an electron system is. Some of the most interesting solids straddle the boundary between localized and delocalized, e.g. the high-temperature superconductors. The bulk of the band calculations available today is based on local density functional (DF) theory. Even though the Kohn-Sham eigenvalues from that theory do not represent the outcome of a band-mapping experiment, they are remarkably similar to the bands mapped via photoemission. Strictly speaking, one should use an excited state calculation that takes the solid`s many-body screening response to the hole created in photoemission into account. Diamond is a useful prototype semiconductor because of its low atomic number and large band width, which has made it a long-time favorite for testing band theory. Yet, the two experimental values of the band width of diamond have error bars of {+-}1 eV and differ by 3.2 eV. To obtain an accurate valence band width for diamond, the authors use a band-mapping method that collects momentum distributions instead of the usual energy distributions. This method has undergone extensive experimental and theoretical tests in determining the band width of lithium fluoride. An efficient, imaging photoelectron spectrometer is coupled with a state-of-the-art undulator beam line at the Advanced Light Source to allow collection of a large number of data sets. Since it takes only a few seconds to take a picture of the photoelectrons emitted into a 84{degrees} cone, the authors can use photon energies as high as 350 eV where the cross section for photoemission from the valence band is already quite low, but the emitted photoelectrons behave free-electron-like. This make its much easier to locate the origin of the inter-band transitions in momentum space.

A theoretical investigation of valence and Rydberg electronic states of acrolein

International Nuclear Information System (INIS)

Aquilante, Francesco; Barone, Vincenzo; Roos, Bjoern O.

2003-01-01

The main features of the ultraviolet spectrum of acrolein have been studied by a multireference perturbative treatment and by a time dependent density functional approach. The valence and Rydberg transition energies have been calculated and the assignment of the experimental bands has been clarified. The different relaxation trends of the three lowest singlet and triplet excited states have been analyzed by unconstrained geometry optimizations. This has allowed, in particular, the characterization of a twisted 3 (ππ*) state, which is crucial for the interesting photophysics and photochemistry of the acrolein molecule and, more generally, of the α,β-enones. Solvatochromic shifts in aqueous solution have been investigated using a combined discrete/continuum approach based on the so called polarizable continuum model. The experimental trends are well reproduced by this approach and a closer degeneracy in the triplet manifold has been detected in solution with respect to gas phase

Valence evaluation with approaching or withdrawing cues: directly testing valence-arousal conflict theory.

Science.gov (United States)

Wang, Yan Mei; Li, Ting; Li, Lin

2017-07-19

The valence-arousal conflict theory assumes that both valence and arousal will trigger approaching or withdrawing tendencies. It also predicts that the speed of processing emotional stimuli will depend on whether valence and arousal trigger conflicting or congruent motivational tendencies. However, most previous studies have provided evidence of the interaction between valence and arousal only, and have not provided direct proof of the interactive links between valence, arousal and motivational tendencies. The present study provides direct evidence for the relationship between approach-withdrawal tendencies and the valence-arousal conflict. In an empirical test, participants were instructed to judge the valence of emotional words after visual-spatial cues that appeared to be either approaching or withdrawing from participants. A three-way interaction (valence, arousal, and approach-withdrawal tendency) was observed such that the response time was shorter if participants responded to a negative high-arousal stimulus after a withdrawing cue, or to a positive low-arousal stimulus after an approaching cue. These findings suggest that the approach-withdrawal tendency indeed plays a crucial role in valence-arousal conflict, and that the effect depends on the congruency of valence, arousal and tendency at an early stage of processing.

Valence instabilities as a source of actinide system inconsistencies

International Nuclear Information System (INIS)

Sandenaw, T.A.

1979-01-01

Light actinide elements alone, and in some of their alloys, may exist as a static or dynamic mixture of two configurations. Such a state can explain both a resistivity maximum and lack of magnetic order observed in so many actinide materials, and still be compatible with the existence of f-electrons in narrow bands. Impurity elements may stabilize slightly different intermediate valence states in U, Np, and Pu, thus contributing to inconsistencies in published results. The physical property behavior of mixed-valence, rare-earth compounds is very much like that observed in development of antiphase (martensitic) structures. Martensitic transformations in U, Np, and Pu, from high-temperature b. c. c. to alpha phase, may be a way of ordering an alloy-like metal of mixed or intermediate valence. The relative stability of each phase structure may depend upon its electron-valence ratio. A Hubbard model for electron correlations in a narrow energy band has been invoked in most recent theories for explaining light actinide behavior. Such a model may also be applicable to crystal symmetry changes in martensitic transformations in actinides

Continuous Flow-Resonance Raman Spectroscopy of an Intermediate Redox State of Cytochrome-C

DEFF Research Database (Denmark)

Forster, M.; Hester, R. E.; Cartling, B.

1982-01-01

An intermediate redox state of cytochrome c at alkaline pH, generated upon rapid reduction by sodium dithionite, has been observed by resonance Raman (RR) spectroscopy in combination with the continuous flow technique. The RR spectrum of the intermediate state is reported for excitation both...... in the (alpha, beta) and the Soret optical absorption band. The spectra of the intermediate state are more like those of the stable reduced form than those of the stable oxidized form. For excitation of 514.5 nm, the most prominent indication of an intermediate state is the wave-number shift of one RR band from...... 1,562 cm-1 in the stable oxidized state through 1,535 cm-1 in the intermediate state to 1,544 cm-1 in the stable reduced state. For excitation at 413.1 nm, a band, present at 1,542 cm-1 in the stable reduced state but not present in the stable oxidized state, is absent in the intermediate state. We...

Control of electron transfer in the cytochrome system of mitochondria by pH, transmembrane pH gradient and electrical potential. The cytochromes b-c segment.

Science.gov (United States)

Papa, S; Lorusso, M; Izzo, G; Capuano, F

1981-02-15

1. A study is presented of the effects of pH, transmembrane pH gradient and electrical potential on oxidoreductions of b and c cytochromes in ox heart mitochondria and 'inside-out' submitochondrial particles. 2. Kinetic analysis shows that, in mitochondria at neutral pH, there is a restraint on the aerobic oxidation of cytochrome b566 with respect to cytochrome b562. Valinomycin plus K+ accelerates cytochrome b566 oxidation and retards net oxidation of cytochrome b562. At alkaline pH the rate of cytochrome b566 oxidation approaches that of cytochrome b562 and the effects of valinomycin on b cytochromes are impaired. 3. At slightly acidic pH, oxygenation of antimycin-supplemented mitochondria causes rapid reduction of cytochrome b566 and small delayed reduction of cytochrome b562. Valinomycin or a pH increase in the medium promote reduction of cytochrome b562 and decrease net reduction of cytochrome b566. 4. Addition of valinomycin to mitochondria and submitochondrial particles in the respiring steady state causes, at pH values around neutrality, preferential oxidation of cytochrome b566 with respect to cytochrome b562. The differential effect of valinomycin on oxidation of cytochromes b566 and b562 is enhanced by substitution of 1H2O of the medium with 2H2O and tends to disappear as the pH of the medium is raised to alkaline values. 5. Nigericin addition in the aerobic steady state causes, both in mitochondria and submitochondrial particles, preferential oxidation of cytochrome b562 with respect to cytochrome b566. This is accompanied by c cytochrome oxidation in mitochondria but c cytochrome reduction in submitochondrial particles. 6. In mitochondria as well as in submitochondrial particles, the aerobic transmembrane potential (delta psi) does not change by raising the pH of the external medium from neutrality to alkalinity. The transmembrane pH gradient (delta pH) on the other hand, decrease slightly. 7. The results presented provide evidence that the delta psi

Resonant inelastic x-ray scattering and photoemission measurement of O2: Direct evidence for dependence of Rydberg-valence mixing on vibrational states in O 1s → Rydberg states

Science.gov (United States)

Gejo, T.; Oura, M.; Tokushima, T.; Horikawa, Y.; Arai, H.; Shin, S.; Kimberg, V.; Kosugi, N.

2017-07-01

High-resolution resonant inelastic x-ray scattering (RIXS) and low-energy photoemission spectra of oxygen molecules have been measured for investigating the electronic structure of Rydberg states in the O 1s → σ* energy region. The electronic characteristics of each Rydberg state have been successfully observed, and new assignments are made for several states. The RIXS spectra clearly show that vibrational excitation is very sensitive to the electronic characteristics because of Rydberg-valence mixing and vibronic coupling in O2. This observation constitutes direct experimental evidence that the Rydberg-valence mixing characteristic depends on the vibrational excitation near the avoided crossing of potential surfaces. We also measured the photoemission spectra of metastable oxygen atoms (O*) from O2 excited to 1s → Rydberg states. The broadening of the 4p Rydberg states of O* has been found with isotropic behavior, implying that excited oxygen molecules undergo dissociation with a lifetime of the order of 10 fs in 1s → Rydberg states.

On the valence state of Yb and Ce in transition metal intermetallic compounds

International Nuclear Information System (INIS)

Boer, F.R. de; Dijkman, W.H.; Mattens, W.C.M.

1979-01-01

In the pure state Yb is a divalent metal, similar to Ca; in alloys it can become trivalent like the majority of the rare earth metals. Using a value of 38 kJ (mol Yb) -1 for the energy difference between divalent and trivalent Yb metal and using model calculations for the heat of formation of intermetallic compounds, the authors are able to account for the existing information on the valence state of Yb in transition metal compounds. A similar analysis of compounds of Ce with transition metals shows that a model in which the 4f electron is treated as a core electron, i.e. being absent in the tetravalent modification of Ce and present as a fully localized electron in trivalent Ce, does not apply. (Auth.)

Semiempirical search for oxide superconductors based on bond valence sums

International Nuclear Information System (INIS)

Tanaka, S.; Fukushima, N.; Niu, H.; Ando, K.

1992-01-01

Relationships between crystal structures and electronic states of layered transition-metal oxides are analyzed in the light of bond valence sums. Correlations between the superconducting transition temperature T c and the bond-valence-sum parameters are investigated for the high-T c cuprate compounds. Possibility of making nonsuperconducting oxides superconducting is discussed. (orig.)

Importance-truncated shell model for multi-shell valence spaces

Energy Technology Data Exchange (ETDEWEB)

Stumpf, Christina; Vobig, Klaus; Roth, Robert [Institut fuer Kernphysik, TU Darmstadt (Germany)

2016-07-01

The valence-space shell model is one of the work horses in nuclear structure theory. In traditional applications, shell-model calculations are carried out using effective interactions constructed in a phenomenological framework for rather small valence spaces, typically spanned by one major shell. We improve on this traditional approach addressing two main aspects. First, we use new effective interactions derived in an ab initio approach and, thus, establish a connection to the underlying nuclear interaction providing access to single- and multi-shell valence spaces. Second, we extend the shell model to larger valence spaces by applying an importance-truncation scheme based on a perturbative importance measure. In this way, we reduce the model space to the relevant basis states for the description of a few target eigenstates and solve the eigenvalue problem in this physics-driven truncated model space. In particular multi-shell valence spaces are not tractable otherwise. We combine the importance-truncated shell model with refined extrapolation schemes to approximately recover the exact result. We present first results obtained in the importance-truncated shell model with the newly derived ab initio effective interactions for multi-shell valence spaces, e.g., the sdpf shell.

Valence, magnetism and conduction in the intermediate valence compounds: the case SmB6

International Nuclear Information System (INIS)

Derr, J.

2006-09-01

In some rare earth based compounds, the 4f level is situated so close to the Fermi level that the valence of the compound can become intermediate between two integer values. The so called 'intermediate valence' compound of Samarium hexaboride (SmB 6 ) is one typical example of the exciting physics which can result from this quantum equilibrium between two valence configurations. The first configuration (Sm 2+ ) corresponds to an insulating and non magnetic state whereas the second one (Sm 3+ ) would theoretically give a magnetic and metallic ground state. This dissertation deals with the influence of pressure on this equilibrium. Specific heat measurements under pressure evidenced a new long range magnetic ordering for pressures higher than p c ∼ 10 GPa. On another hand, transport measurements measured for the first time in good conditions of hydrostatics found a reliable and reproducible critical pressure for the insulator to metal transition equal to p c . The phase diagram of SmB 6 is now well known and the observation for the first time of a magnetic anomaly in the high pressure resistivity curves certifies that the onset of the magnetic phase really coincide with the closure of the gap. This change at the critical pressure p c is discussed in a general frame taking into account the Kondo lattice temperature as a key parameter for the renormalization of the wavefunction from one integer configuration to the other whereas the valence itself is still intermediate. This general idea seems to be valid also for other systems studied in this dissertation like SmS or TmSe and could even be valid for more general cases (Ytterbium, Cerium). In the same time, resistivity measurements under uniaxial stress were undertaken. The result is a strong anisotropy effect observed on the pressure dependence of the residual resistivity in the compound SmB 6 . The comparison with the transport under hydrostatic conditions enables us to consider a new idea for the nature of the gap

Single molecule activity measurements of cytochrome P450 oxidoreductase reveal the existence of two discrete functional states

DEFF Research Database (Denmark)

Laursen, Tomas; Singha, Aparajita; Rantzau, Nicolai

2014-01-01

450 enzymes. Measurements and statistical analy-sis of individual catalytic turnover cycles shows POR to sample at least two major functional states. This phenotype may underlie regulatory interactions with different cytochromes P450 but to date remained masked in bulk kinetics. To ensure that we...

Investigation of the Impact of Different Terms in the Second Order Hamiltonian on Excitation Energies of Valence and Rydberg States.

Science.gov (United States)

Tajti, Attila; Szalay, Péter G

2016-11-08

Describing electronically excited states of molecules accurately poses a challenging problem for theoretical methods. Popular second order techniques like Linear Response CC2 (CC2-LR), Partitioned Equation-of-Motion MBPT(2) (P-EOM-MBPT(2)), or Equation-of-Motion CCSD(2) (EOM-CCSD(2)) often produce results that are controversial and are ill-balanced with their accuracy on valence and Rydberg type states. In this study, we connect the theory of these methods and, to investigate the origin of their different behavior, establish a series of intermediate variants. The accuracy of these on excitation energies of singlet valence and Rydberg electronic states is benchmarked on a large sample against high-accuracy Linear Response CC3 references. The results reveal the role of individual terms of the second order similarity transformed Hamiltonian, and the reason for the bad performance of CC2-LR in the description of Rydberg states. We also clarify the importance of the T̂ 1 transformation employed in the CC2 procedure, which is found to be very small for vertical excitation energies.

Cytochrome C effect on gamma-ray efficiency on barley seeds at different metabolic states

International Nuclear Information System (INIS)

Yankulov, M.

1981-01-01

Radiobiological studies of the effect of gamma-rays on the barley seeds were performed. It was shown that the different metabolic states of the seeds do not modify the effect of the independent treatment with cytochrome C, while the action of the gamma-rays is markedly modified. With the increase in the preliminary seed soaking time in H 2 O, the total lethality in the case of irradiated treatments rises from 54.10% to 91.00% and that of sterility to 13.13 and 57.44% for 12 and 72 hrs, respectively. The preliminary and post-irradiation treatment of seeds with cytochrome C markedly reduces the effect of gamma-rays, calculated by the criteria of general lethality and sterility, the trend towards an increase in the sensitivity with the increase in the extention of the preliminary soaking time of seeds in water being preserved. Preliminary soaking in the seeds in water also modifies the mutagenic effect of gamma-rays to a considerable extent. (author)

Hole energy and momentum distributions in valence bands

International Nuclear Information System (INIS)

Laan, G. van der.

1982-01-01

In order to understand the electrical and magnetic properties of solids, the knowledge of the density of states and the dispersion relation of the valence bands is indispensable. This thesis offers some alternative methods to obtain information about the nature of the valence band. Part A deals with the energy distribution of the photoelectrons. A simple model, which explains the core hole satellite structure in compounds with large correlation effects between the valence band holes and the created photo-hole, is outlined. CuCl, CuX 2 (X = F Cl and Br) are studied, by photoemission and Auger electron spectroscopies in determining the valence band properties. Part B deals with the simultaneous measurement of the energy and the wave vector of the emitted electrons. A practical example is given for the determination of the dispersion relation in copper. The measurements of a surface resonance band and the distribution of the secondary electrons are also reported. (Auth.)

Cytochrome oxidase assembly does not require catalytically active cytochrome C.

Science.gov (United States)

Barrientos, Antoni; Pierre, Danielle; Lee, Johnson; Tzagoloff, Alexander

2003-03-14

Cytochrome c oxidase (COX), the terminal enzyme of the mitochondrial respiratory chain, catalyzes the transfer of electrons from reduced cytochrome c to molecular oxygen. COX assembly requires the coming together of nuclear- and mitochondrial-encoded subunits and the assistance of a large number of nuclear gene products acting at different stages of maturation of the enzyme. In Saccharomyces cerevisiae, expression of cytochrome c, encoded by CYC1 and CYC7, is required not only for electron transfer but also for COX assembly through a still unknown mechanism. We have attempted to distinguish between a functional and structural requirement of cytochrome c in COX assembly. A cyc1/cyc7 double null mutant strain was transformed with the cyc1-166 mutant gene (Schweingruber, M. E., Stewart, J. W., and Sherman, F. (1979) J. Biol. Chem. 254, 4132-4143) that expresses stable but catalytically inactive iso-1-cytochrome c. The COX content of the cyc1/cyc7 double mutant strain harboring non-functional iso-1-cytochrome c has been characterized spectrally, functionally, and immunochemically. The results of these studies demonstrate that cytochrome c plays a structural rather than functional role in assembly of cytochrome c oxidase. In addition to its requirement for COX assembly, cytochrome c also affects turnover of the enzyme. Mutants containing wild type apocytochrome c in mitochondria lack COX, suggesting that only the folded and mature protein is able to promote COX assembly.

Denatured states of yeast cytochrome c induced by heat and guanidinium chloride are structurally and thermodynamically different.

Science.gov (United States)

Zaidi, Sobia; Haque, Md Anzarul; Ubaid-Ullah, Shah; Prakash, Amresh; Hassan, Md Imtaiyaz; Islam, Asimul; Batra, Janendra K; Ahmad, Faizan

2017-05-01

A sequence alignment of mammalian cytochromes c with yeast iso-1-cytochrome c (y-cyt-c) shows that the yeast protein contains five extra N-terminal residues. We have been interested in understanding the question: What is the role of these five extra N-terminal residues in folding and stability of the protein? To answer this question we have prepared five deletants of y-cyt-c by sequentially removing these extra residues. During our studies on the wild type (WT) protein and its deletants, we observed that the amount of secondary structure in the guanidinium chloride (GdmCl)-induced denatured (D) state of each protein is different from that of the heat-induced denatured (H) state. This finding is confirmed by the observation of an additional cooperative transition curve of optical properties between H and D states on the addition of different concentrations of GdmCl to the already heat denatured WT y-cyt-c and its deletants at pH 6.0 and 68°C. For each protein, analysis of transition curves representing processes, native (N) state ↔ D state, N state ↔ H state, and H state ↔ D state, was done to obtain Gibbs free energy changes associated with all the three processes. This analysis showed that, for each protein, thermodynamic cycle accommodates Gibbs free energies associated with transitions between N and D states, N and H states, and H and D states, the characteristics required for a thermodynamic function. All these experimental observations have been supported by our molecular dynamics simulation studies.

Direct Electron Impact Excitation of Rydberg-Valence States of Molecular Nitrogen

Science.gov (United States)

Malone, C. P.; Johnson, P. V.; Liu, X.; Ajdari, B.; Muleady, S.; Kanik, I.; Khakoo, M. A.

2012-12-01

Collisions between electrons and neutral N2 molecules result in emissions that provide an important diagnostic probe for understanding the ionospheric energy balance and the effects of space weather in upper atmospheres. Also, transitions to singlet ungerade states cause N2 to be a strong absorber of solar radiation in the EUV spectral range where many ro-vibrational levels of these Rydberg-valence (RV) states are predissociative. Thus, their respective excitation and emission cross sections are important parameters for understanding the [N]/[N2] ratio in the thermosphere of nitrogen dominated atmospheres. The following work provides improved constraints on absolute and relative excitation cross sections of numerous RV states of N2, enabling more physically accurate atmospheric modeling. Here, we present recent integral cross sections (ICSs) for electron impact excitation of RV states of N2 [6], which were based on the differential cross sections (DCSs) derived from electron energy-loss (EEL) spectra of [5]. This work resulted in electronic excitation cross sections over the following measured vibrational levels: b 1Πu (v‧=0-14), c3 1Πu (v‧=0-3), o3 1Πu (v‧=0-3), b‧ 1Σu+ (v‧=0-10), c‧4 1Σu+ (v‧=0-3), G 3Πu (v‧=0-3), and F 3Πu (v‧=0-3). We further adjusted the cross sections of the RV states by extending the vibronic contributions to unmeasured v‧-levels via the relative excitation probabilities (REPs) as discussed in [6]. This resulted in REP-scaled ICSs over the following vibrational levels for the singlet ungerade states: b(0-19), c3(0-4), o3(0-4), b‧(0-16), and c‧4(0-8). Comparison of the ICSs of [6] with available EEL based measurements, theoretical calculations, and emission based work generally shows good agreement within error estimations, except with the recent reevaluation provided by [1]. Further, we have extended these results, using the recent EEL data of [3], to include the unfolding of better resolved features above ~13

Solution NMR study of the yeast cytochrome c peroxidase: cytochrome c interaction

Energy Technology Data Exchange (ETDEWEB)

Volkov, Alexander N., E-mail: ovolkov@vub.ac.be; Nuland, Nico A. J. van [Vrije Universiteit Brussel, Jean Jeener NMR Centre, Structural Biology Brussels (Belgium)

2013-07-15

Here we present a solution NMR study of the complex between yeast cytochrome c (Cc) and cytochrome c peroxidase (CcP), a paradigm for understanding the biological electron transfer. Performed for the first time, the CcP-observed heteronuclear NMR experiments were used to probe the Cc binding in solution. Combining the Cc- and CcP-detected experiments, the binding interface on both proteins was mapped out, confirming that the X-ray structure of the complex is maintained in solution. Using NMR titrations and chemical shift perturbation analysis, we show that the interaction is independent of the CcP spin-state and is only weakly affected by the Cc redox state. Based on these findings, we argue that the complex of the ferrous Cc and the cyanide-bound CcP is a good mimic of the catalytically-active Cc-CcP compound I species. Finally, no chemical shift perturbations due to the Cc binding at the low-affinity CcP site were observed at low ionic strength. We discuss possible reasons for the absence of the effects and outline future research directions.

Exchange Coupling Interactions from the Density Matrix Renormalization Group and N-Electron Valence Perturbation Theory: Application to a Biomimetic Mixed-Valence Manganese Complex.

Science.gov (United States)

Roemelt, Michael; Krewald, Vera; Pantazis, Dimitrios A

2018-01-09

The accurate description of magnetic level energetics in oligonuclear exchange-coupled transition-metal complexes remains a formidable challenge for quantum chemistry. The density matrix renormalization group (DMRG) brings such systems for the first time easily within reach of multireference wave function methods by enabling the use of unprecedentedly large active spaces. But does this guarantee systematic improvement in predictive ability and, if so, under which conditions? We identify operational parameters in the use of DMRG using as a test system an experimentally characterized mixed-valence bis-μ-oxo/μ-acetato Mn(III,IV) dimer, a model for the oxygen-evolving complex of photosystem II. A complete active space of all metal 3d and bridge 2p orbitals proved to be the smallest meaningful starting point; this is readily accessible with DMRG and greatly improves on the unrealistic metal-only configuration interaction or complete active space self-consistent field (CASSCF) values. Orbital optimization is critical for stabilizing the antiferromagnetic state, while a state-averaged approach over all spin states involved is required to avoid artificial deviations from isotropic behavior that are associated with state-specific calculations. Selective inclusion of localized orbital subspaces enables probing the relative contributions of different ligands and distinct superexchange pathways. Overall, however, full-valence DMRG-CASSCF calculations fall short of providing a quantitative description of the exchange coupling owing to insufficient recovery of dynamic correlation. Quantitatively accurate results can be achieved through a DMRG implementation of second order N-electron valence perturbation theory (NEVPT2) in conjunction with a full-valence metal and ligand active space. Perspectives for future applications of DMRG-CASSCF/NEVPT2 to exchange coupling in oligonuclear clusters are discussed.

B-site cation order/disorder and their valence states in Ba3MnNb2O9 perovskite oxide

Science.gov (United States)

Xin, Yan; Huang, Qing; Shafieizadeh, Zahra; Zhou, Haidong

2018-06-01

Polycrystalline samples Ba3MnNb2O9 synthesized by solid state reaction and single crystal samples grown by optical floating zone have been characterized using scanning transmission electron microscopy and electron energy loss spectroscopy. Three types of B-site Mn and Nb ordering phase are observed: fully ordered 1Mn:2Nb; fully disordered; nano-sized 1Mn:1Nb ordered. No electronic structure change for crystals with different ordering/disordering. The Mn valence is determined to be 2+, and Nb valence is 5+. Oxygen 2p orbitals hybridize with Mn 3d and Nb 4d orbitals. Factors that affect the electron energy loss near edge structures of transition metal white-lines in electron energy loss spectroscopy are explicitly illustrated and discussed.

Study of iron valence state and position in sub-site by Moessbauer spectroscopy

International Nuclear Information System (INIS)

Uhm, Young Rang; Lim, Jae Cheong; KIm, Chul Sung; Son, Kwang Jae

2014-01-01

The magnetic ordering temperature and the magnitude of the magnetic fields at the iron sites of YIG can be influenced by substituting, either partially or totally, the Fe 3+ ions at the octahedral and/or the tetrahedral sites with magnetic or diamagnetic ions, and/or by substitution the Y 3+ ions at the dodecahedral sites with magnetic rare earth ions. It has been known for some time that Moessbauer spectroscopy is a powerful method by which iron-containing garnets can be studied. We report here on the synthesis of the compounds with garnet-related structures of composition Y 3 Fe 4.5 Cr 0.5 O 12 and its examination by 57 Fe Moessbauer spectroscopy. The chromium in compounds of the Y 3 Fe 4.5 Cr 0.5 O 12 is distributed at an octahedral site. The Moessbauer spectra can be analyzed using 3 or 4 sets of six Lorentzians with increasing amount of Cr 3+ compounds in this system. It results from the distribution ( 4 C n ) of Fe 3+ and Cr 3+ at an octahedral site. A comparative study of ferrous tablets of Dynabi was carried out using Moessbauer spectroscopy. The obtained results revealed the presence of ferrous (Fe 2+ ) gluconate and ferrous fumarate in a sample. This observation is important to better control the iron state in such medicaments because their pharmaceutical effect in the body is related to the form and valence of iron. The Cr-containing yttrium iron garnet (YIG), and the exchange interactions and site distributions were studied using 57 Fe Moessbauer spectroscopy. The obtained results revealed the presence of ferrous (Fe 2+ ) gluconate and ferrous fumarate in the sample. This observation is important better control the iron state in such medicaments because their pharmaceutical effect in the body is related to the form and valence of iron

Vanadium K XANES of synthetic olivine: Valence determinations and crystal orientation effects

International Nuclear Information System (INIS)

Sutton, S.R.; Newville, M.

2005-01-01

Vanadium can exist in a large number of valence states in nature (2+?, 3+, 4+ and 5+) and determinations of V valence is therefore valuable in defining the oxidation states of earth and planetary materials over a large redox range. Synchrotron-based x-ray absorption near edge structure (XANES) spectroscopy is well-suited for measurements of V valence with ∼micrometer spatial resolution and ∼ppm elemental sensitivity. Applications of microXANES have been demonstrated for basaltic glasses. Applications to minerals are feasible but complicated by orientation effects (e.g. due to polarization of the synchrotron x-ray beam) and some results for spinel have been reported. Here we report initial results for olivine from laboratory crystallization ex-periments. The goal is to define the valence partition-ing between olivine and melt and quantify the magnitude of orientation effects, the latter tested by measuring grains at a variety of orientations in the same charge.

Development of hard X-ray photoelectron SPLEED-based spectrometer applicable for probing of buried magnetic layer valence states

Energy Technology Data Exchange (ETDEWEB)

Kozina, Xeniya, E-mail: kozina@uni-mainz.de [Japan Synchrotron Radiation Research Institute, SPring-8, Hyogo 679-5198 (Japan); Ikenaga, Eiji [Japan Synchrotron Radiation Research Institute, SPring-8, Hyogo 679-5198 (Japan); Viol Barbosa, Carlos Eduardo; Ouardi, Siham; Karel, Julie [Max-Planck-Institut für Chemische Physik fester Stoffe, 01187 Dresden (Germany); Yamamoto, Masafumi [Division of Electronics for Informatics, Hokkaido University, Sapporo 060-0814 (Japan); Kobayashi, Keisuke [Japan Atomic Energy Agency, SPring-8, Hyogo 679-5148 (Japan); Elmers, Hans Joachim; Schönhense, Gerd [Institut für Physik, Johannes Gutenberg – Universität, 55099 Mainz (Germany); Felser, Claudia [Max-Planck-Institut für Chemische Physik fester Stoffe, 01187 Dresden (Germany)

2016-08-15

Highlights: • A high-voltage compatible spin-HAXPES detector based on SPLEED from W(001) has been developed. • Magnetic properties of a TMR device were studied by core-level photoemission on the Fe 2p{sub 3/2} states. • The developed instrument enabled probing of buried layers in the region of the valence states. - Abstract: A novel design of high-voltage compatible polarimeter for spin-resolved hard X-ray photoelectron spectroscopy (Spin-HAXPES) went into operation at beamline BL09XU of SPring-8 in Hyogo, Japan. The detector is based on the well-established principle of electron diffraction from a W(001) single-crystal at a scattering energy of 103.5 eV. It's special feature is that it can be operated at a high negative bias potential up to 10 kV, necessary to access the HAXPES range. The polarimeter is operated behind a large hemispherical analyzer (Scienta R-4000). It was optimized for high transmission of the transfer optics. A delay-line detector (20 mm dia.) is positioned at the exit plane of the analyzer enabling conventional multichannel intensity spectroscopy simultaneously with single-channel spin analysis. The performance of the combined setup is demonstrated by the spin-resolved data for the valence-region of a FeCo functional layer of a tunneling device, buried beneath 3 nm of oxidic material. The well-structured spin polarization spectrum validates Spin-HAXPES in the valence energy range as powerful method for bulk electronic structure analysis. The spin polarization spectrum exhibits a rich structure, originating from clearly discernible transitions in the majority and minority partial spin spectra.

Measurement of valence band structure in arbitrary dielectric films

International Nuclear Information System (INIS)

Uhm, Han S.; Choi, Eun H.

2012-01-01

A new way of measuring the band structure of various dielectric materials using the secondary electron emission from Auger neutralization of ions is introduced. The first example of this measurement scheme is the magnesium oxide (MgO) films with respect to the application of the films in the display industries. The density of state in the valence bands of MgO film and MgO film with a functional layer (FL) deposited over a dielectric surface reveals that the density peak of film with a FL is considerably less than that of film, thereby indicating a better performance of MgO film with functional layer in display devices. The second example of the measurement is the boron-zinc oxide (BZO) films with respect to the application of the films to the development of solar cells. The measurement of density of state in BZO film suggests that a high concentration of boron impurity in BZO films may enhance the transition of electrons and holes through the band gap from the valence to the conduction band in zinc oxide crystals; thereby improving the conductivity of the film. Secondary electron emission by the Auger neutralization of ions is highly instrumental for the determination of the density of states in the valence band of dielectric materials.

Valence fluctuations between two magnetic configurations

International Nuclear Information System (INIS)

Mazzaferro, J.O.

1982-01-01

The subject of this work is the study of a microscopic model which describes TmSe through its most important feature, i.e.: the valence fluctuations between two magnetic configurations. Chapter I is a general review of the most important physical properties of rare-earth systems with intermediate valence (I.V.) and a general description of experimental results and theoretical models on Tm compounds. In Chapter II the Hamiltonian model is discussed and the loss of rotational invariance is also analyzed. Chapter III is devoted to the study of non-stoichiometric Tsub(x)Se compounds. It is shown that these compounds can be considered as a mixture of TmSe (I.V. system) and Tm 3+ 0.87Se. Chapter IV is devoted to the calculation of spin-and charge susceptibilities. The results obtained permit to explain the essential features of the neutron scattering spectrum in TmSe. In Chapter V, an exactly solvable periodic Hamiltonian is presented. From the experimental results, some fundamental features are deduced to describe TmSe as an intermediate valence system whose two accessible ionic configurations are magnetic (degenerated fundamental state). (M.E.L) [es

The mechanism of electron gating in proton pumping cytochrome c oxidase: the effect of pH and temperature on internal electron transfer.

Science.gov (United States)

Brzezinski, P; Malmström, B G

1987-10-29

Electron-transfer reactions following flash photolysis of the mixed-valence cytochrome oxidase-CO complex have been measured at 445, 598 and 830 nm between pH 5.2 and 9.0 in the temperature range of 0-25 degrees C. There is a rapid electron transfer from the cytochrome a3-CuB pair to CuA (time constant: 14200 s-1), which is followed by a slower electron transfer to cytochrome a. Both the rate and the amplitude of the rapid phase are independent of pH, and the rate in the direction from CuA to cytochrome a3-CuB is practically independent of temperature. The second phase depends strongly on pH due to the titration of an acid-base group with pKa = 7.6. The equilibrium at pH 7.4 corresponds to reduction potentials of 225 and 345 mV for cytochrome a and a3, respectively, from which it is concluded that the enzyme is in a different conformation compared to the fully oxidized form. The results have been used to suggest a series of reaction steps in a cycle of the oxidase as a proton pump. Application of the electron-transfer theory to the temperature-dependence data suggests a mechanism for electron gating in the pump. Reduction of both cytochrome a and CuA leads to a conformational change, which changes the structure of cytochrome a3-CuB in such a way that the reorganizational barrier for electron transfer is removed and the driving force is increased.

Valence electron momentum distributions in cadmium

International Nuclear Information System (INIS)

Frost, L.; Weigold, E.; Mitroy, J.

1982-08-01

The valence 5s and 4d electron momentum distributions in cadmium have been measured using noncoplanar symmetric (e, 2e) electron coincidence spectroscopy at a total energy of 1200eV. They are in close agreement with Hartree-Fock momentum distributions both in shape and relative magnitudes. Some satellite lines of very low intensity have been detected. A CI calculation of the Cd ground state and several Cd + ion states has been carried out to predict cross reactions for the ground state and various satellite transitions. The predictions are in agreement with the data

Valence and Magnetic Transitions in YbMn2Ge2-Applied Pressure

International Nuclear Information System (INIS)

Hofmann, M.; Link, P.; Campbell, S.J.; Goncharenko, I.

2005-01-01

Full text: Rare-earth intermetallic compounds containing ytterbium exhibit a wide range of interesting and unusual physical and magnetic properties. This occurs mainly as a result of their mixed valence states (II/III) or changes from one valence state to the other. We have recently determined the magnetic structures of tetragonal YbMn 2 Ge 2 (I4/mmm) by powder neutron diffraction experiments and demonstrated that YbMn 2 Ge 2 has a planar antiferromagnetic structure below T N1 ∼ 510 K with a canted antiferromagnetic structure below T N2 ∼ 185 K. As applied pressure favours changes in the valence character of intermediate valence systems and correspondingly influences the magnetic behaviour, we have investigated the effects of applied pressure on YbMn 2 Ge 2 . Analyses of our in situ neutron diffraction experiments (T=1.5-300 K; p=0-2.7 GPa), reveal a distinct change in magnetic structure and a sharp drop in the a-lattice parameter above ∼ 1.4 GPa with the changes associated with a valence transition. A full account of these effects will be discussed in relation to our current photoelectron spectroscopy measurements of YbMn 2 Ge 2 . (authors)

Iron valence in double-perovskite (Ba,Sr,Ca)2FeMoO6: isovalent substitution effect

International Nuclear Information System (INIS)

Yasukawa, Y.; Linden, J.; Chan, T.S.; Liu, R.S.; Yamauchi, H.; Karppinen, M.

2004-01-01

In the Fe-Mo based B-site ordered double-perovskite, A 2 FeMoO 6.0 , with iron in the mixed-valence II/III state, the valence value of Fe is not precisely fixed at 2.5 but may be fine-tuned by means of applying chemical pressure at the A-cation site. This is shown through a systematic 57 Fe Moessbauer spectroscopy study using a series of A 2 FeMoO 6.0 [A=(Ba,Sr) or (Sr,Ca)] samples with high degree of Fe/Mo order, the same stoichiometric oxygen content and also almost the same grain size. The isomer shift values and other hyperfine parameters obtained from the Moessbauer spectra confirm that Fe remains in the mixed-valence state within the whole range of A constituents. However, upon increasing the average cation size at the A site the precise valence of Fe is found to decrease such that within the A=(Ba,Sr) regime the valence of Fe is closer to II, while within the A=(Sr,Ca) regime it is closer to the actual mixed-valence II/III state. As the valence of Fe approaches II, the difference in charges between Fe and Mo increases, and parallel with this the degree of Fe/Mo order increases. Additionally, for the less-ordered samples an increased tendency of clustering of the antisite Fe atoms is deduced from the Moessbauer data

Cytochrome c1 exhibits two binding sites for cytochrome c in plants.

Science.gov (United States)

Moreno-Beltrán, Blas; Díaz-Quintana, Antonio; González-Arzola, Katiuska; Velázquez-Campoy, Adrián; De la Rosa, Miguel A; Díaz-Moreno, Irene

2014-10-01

In plants, channeling of cytochrome c molecules between complexes III and IV has been purported to shuttle electrons within the supercomplexes instead of carrying electrons by random diffusion across the intermembrane bulk phase. However, the mode plant cytochrome c behaves inside a supercomplex such as the respirasome, formed by complexes I, III and IV, remains obscure from a structural point of view. Here, we report ab-initio Brownian dynamics calculations and nuclear magnetic resonance-driven docking computations showing two binding sites for plant cytochrome c at the head soluble domain of plant cytochrome c1, namely a non-productive (or distal) site with a long heme-to-heme distance and a functional (or proximal) site with the two heme groups close enough as to allow electron transfer. As inferred from isothermal titration calorimetry experiments, the two binding sites exhibit different equilibrium dissociation constants, for both reduced and oxidized species, that are all within the micromolar range, thus revealing the transient nature of such a respiratory complex. Although the docking of cytochrome c at the distal site occurs at the interface between cytochrome c1 and the Rieske subunit, it is fully compatible with the complex III structure. In our model, the extra distal site in complex III could indeed facilitate the functional cytochrome c channeling towards complex IV by building a "floating boat bridge" of cytochrome c molecules (between complexes III and IV) in plant respirasome. Copyright © 2014 Elsevier B.V. All rights reserved.

The Role of Cytochromes P450 in Infection

Directory of Open Access Journals (Sweden)

Elisavet Stavropoulou

2018-01-01

Full Text Available Cytochromes are expressed in many different tissues of the human body. They are found mostly in intestinal and hepatic tissues. Cytochromes P450 (CYPs are enzymes that oxidize substances using iron and are able to metabolize a large variety of xenobiotic substances. CYP enzymes are linked to a wide array of reactions including and O-dealkylation, S-oxidation, epoxidation, and hydroxylation. The activity of the typical P450 cytochrome is influenced by a variety of factors, such as genus, environment, disease state, herbicide, alcohol, and herbal medications. However, diet seems to play a major role. The mechanisms of action of dietary chemicals, macro- and micronutrients on specific CYP isoenzymes have been extensively studied. Dietary modulation has effects upon the metabolism of xenobiotics. Cytochromes harbor intra- or interindividual and intra- or interethnic genetic polymorphisms. Bacteria were shown to express CYP-like genes. The tremendous metabolic activity of the microbiota is associated to its abundant pool of CYP enzymes, which catalyze phase I and II reactions in drug metabolism. Disease states, intestinal disturbances, aging, environmental toxic effects, chemical exposures or nutrition modulate the microbial metabolism of a drug before absorption. A plethora of effects exhibited by most of CYP enzymes can resemble those of proinflammatory cytokines and IFNs. Moreover, they are involved in the initiation and persistence of pathologic pain by directly activating sensory neurons and inflammatory cytokines.

Study of iron valence state and position in sub-site by Moessbauer spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Uhm, Young Rang; Lim, Jae Cheong; KIm, Chul Sung [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of); Son, Kwang Jae [Kookmin Univ., Seoul (Korea, Republic of)

2014-05-15

The magnetic ordering temperature and the magnitude of the magnetic fields at the iron sites of YIG can be influenced by substituting, either partially or totally, the Fe{sup 3+} ions at the octahedral and/or the tetrahedral sites with magnetic or diamagnetic ions, and/or by substitution the Y{sup 3+} ions at the dodecahedral sites with magnetic rare earth ions. It has been known for some time that Moessbauer spectroscopy is a powerful method by which iron-containing garnets can be studied. We report here on the synthesis of the compounds with garnet-related structures of composition Y{sub 3}Fe{sub 4.5}Cr{sub 0.5}O{sub 12} and its examination by {sup 57}Fe Moessbauer spectroscopy. The chromium in compounds of the Y{sub 3}Fe{sub 4.5}Cr{sub 0.5}O{sub 12} is distributed at an octahedral site. The Moessbauer spectra can be analyzed using 3 or 4 sets of six Lorentzians with increasing amount of Cr{sup 3+} compounds in this system. It results from the distribution ({sub 4}C{sub n}) of Fe{sup 3+} and Cr{sup 3+} at an octahedral site. A comparative study of ferrous tablets of Dynabi was carried out using Moessbauer spectroscopy. The obtained results revealed the presence of ferrous (Fe{sup 2+}) gluconate and ferrous fumarate in a sample. This observation is important to better control the iron state in such medicaments because their pharmaceutical effect in the body is related to the form and valence of iron. The Cr-containing yttrium iron garnet (YIG), and the exchange interactions and site distributions were studied using {sup 57}Fe Moessbauer spectroscopy. The obtained results revealed the presence of ferrous (Fe{sup 2+}) gluconate and ferrous fumarate in the sample. This observation is important better control the iron state in such medicaments because their pharmaceutical effect in the body is related to the form and valence of iron.

Double-valence-fluctuating molecules and superconductivity

International Nuclear Information System (INIS)

Hirsch, J.E.; Scalapino, D.J.

1985-01-01

We discuss the possibility of ''double-valence-fluctuating'' molecules, having two ground-state configurations differing by two electrons. We propose a possible realization of such a molecule, and experimental ways to look for it. We argue that a weakly coupled array of such molecules should give rise to a strong-coupling Shafroth-Blatt-Butler superconductor, with a high transition temperature

Effect of laser irradiation on the structure and valence states of copper in Cu-phosphate glass by XPS studies

International Nuclear Information System (INIS)

Khattak, G.D.; Mekki, A.; Gondal, M.A.

2010-01-01

The effect of laser irradiation using three different wavelengths (IR, visible and UV) generated from Nd:YAG laser on the local glass structure as well as on the valence state of the copper ions in copper phosphate glass containing CuO with the nominal composition 0.30(CuO)-(0.70)(P 2 O 5 ), has been investigated by X-ray photoelectron spectroscopy (XPS). The presence of asymmetry and satellite peaks in the Cu 2p spectrum for the unirradiated sample is an indication of the presence of two different valence states, Cu 2+ and Cu + . Hence, the Cu 2p 3/2 spectrum was fitted to two Gaussian-Lorentzian peaks and the corresponding ratio, Cu 2+ /Cu total , determined from these relative areas clearly shows that copper ions exist predominately (>86%) in the Cu 2+ state for the unirradiated glass sample under investigation. For the irradiated samples the symmetry and the absence of satellite peaks in the Cu 2p spectra indicate the existence of the copper ions mostly in Cu + state. The O 1s spectra show slight asymmetry for the irradiated as well as unirradiated glass samples which result from two contributions, one from the presence of oxygen atoms in the P-O-P environment (bridging oxygen BO) and the other from oxygen in an P-O-Cu and P=O environment (non-bridging oxygen NBO). The ratio of NBO to total oxygen was found to increase with laser power.

Chromium valences in ureilite olivine and implications for ureilite petrogenesis

Science.gov (United States)

Goodrich, C. A.; Sutton, S. R.; Wirick, S.; Jercinovic, M. J.

2013-12-01

Ureilites are a group of ultramafic achondrites commonly thought to be residues of partial melting on a carbon-rich asteroid. They show a large variation in FeO content (olivine Fo values ranging from ∼74 to 95) that cannot be due to igneous fractionation and suggests instead variation in oxidation state. The presence of chromite in only a few of the most ferroan (Fo 75-76) samples appears to support such a model. MicroXANES analyses were used in this study to determine the valence states of Cr (previously unknown) in olivine cores of 11 main group ureilites. The goal of this work was to use a method that is independent of Fo to determine the oxidation conditions under which ureilites formed, in order to evaluate whether the ureilite FeO-variation is correlated with oxidation state, and whether it is nebular or planetary in origin. Two of the analyzed samples, LEW 88774 (Fo 74.2) and NWA 766 (Fo 76.7) contain primary chromite; two others, LAP 03587 (Fo 74.4) and CMS 04048 (Fo 76.2) contain sub-micrometer-sized exsolutions of chromite + Ca-rich pyroxene in olivine; and one, EET 96328 (Fo 85.2) contains an unusual chromite grain of uncertain origin. No chromite has been observed in the remaining six samples (Fo 77.4-92.3). Chromium in olivine in all eleven samples was found to be dominated by the divalent species, with valences ranging from 2.10 ± 0.02 (1σ) to 2.46 ± 0.04. The non-chromite-bearing ureilites have the most reduced Cr, with a weighted mean valence of 2.12 ± 0.01, i.e., Cr2+/Cr3+ = 7.33. All low-Fo chromite-bearing ureilites have more oxidized Cr, with valences ranging from 2.22 ± 0.03 to 2.46 ± 0.04. EET 96328, whose chromite grain we interpret as a late-crystallizing phase, yielded a reduced Cr valence of 2.15 ± 0.07, similar to the non-chromite-bearing samples. Based on the measured Cr valences, magmatic (1200-1300 °C) oxygen fugacities (fO2) of the non-chromite-bearing samples were estimated to be in the range IW-1.9 to IW-2.8 (assuming

Valence band structure of binary chalcogenide vitreous semiconductors by high-resolution XPS

International Nuclear Information System (INIS)

Kozyukhin, S.; Golovchak, R.; Kovalskiy, A.; Shpotyuk, O.; Jain, H.

2011-01-01

High-resolution X-ray photoelectron spectroscopy (XPS) is used to study regularities in the formation of valence band electronic structure in binary As x Se 100−x , As x S 100−x , Ge x Se 100−x and Ge x S 100−x chalcogenide vitreous semiconductors. It is shown that the highest occupied energetic states in the valence band of these materials are formed by lone pair electrons of chalcogen atoms, which play dominant role in the formation of valence band electronic structure of chalcogen-rich glasses. A well-expressed contribution from chalcogen bonding p electrons and more deep s orbitals are also recorded in the experimental valence band XPS spectra. Compositional dependences of the observed bands are qualitatively analyzed from structural and compositional points of view.

Valence band structure of binary chalcogenide vitreous semiconductors by high-resolution XPS

Energy Technology Data Exchange (ETDEWEB)

Kozyukhin, S., E-mail: sergkoz@igic.ras.ru [Russian Academy of Science, Institute of General and Inorganic Chemistry (Russian Federation); Golovchak, R. [Lviv Scientific Research Institute of Materials of SRC ' Carat' (Ukraine); Kovalskiy, A. [Lehigh University, Department of Materials Science and Engineering (United States); Shpotyuk, O. [Lviv Scientific Research Institute of Materials of SRC ' Carat' (Ukraine); Jain, H. [Lehigh University, Department of Materials Science and Engineering (United States)

2011-04-15

High-resolution X-ray photoelectron spectroscopy (XPS) is used to study regularities in the formation of valence band electronic structure in binary As{sub x}Se{sub 100-x}, As{sub x}S{sub 100-x}, Ge{sub x}Se{sub 100-x} and Ge{sub x}S{sub 100-x} chalcogenide vitreous semiconductors. It is shown that the highest occupied energetic states in the valence band of these materials are formed by lone pair electrons of chalcogen atoms, which play dominant role in the formation of valence band electronic structure of chalcogen-rich glasses. A well-expressed contribution from chalcogen bonding p electrons and more deep s orbitals are also recorded in the experimental valence band XPS spectra. Compositional dependences of the observed bands are qualitatively analyzed from structural and compositional points of view.

In search for an optimal methodology to calculate the valence electron affinities of temporary anions.

Science.gov (United States)

Puiatti, Marcelo; Vera, D Mariano A; Pierini, Adriana B

2009-10-28

Recently, we have proposed an approach for finding the valence anion ground state, based on the stabilization exerted by a polar solvent; the methodology used standard DFT methods and relatively inexpensive basis sets and yielded correct electron affinity (EA) values by gradually decreasing the dielectric constant of the medium. In order to address the overall performance of the new methodology, to find the best conditions for stabilizing the valence state and to evaluate its scope and limitations, we gathered a pool of 60 molecules, 25 of them bearing the conventional valence state as the ground anion and 35 for which the lowest anion state found holds the extra electron in a diffuse orbital around the molecule (non valence state). The results obtained by testing this representative set suggest a very good performance for most species having an experimental EA less negative than -3.0 eV; the correlation at the B3LYP/6-311+G(2df,p) level being y = 1.01x + 0.06, with a correlation index of 0.985. As an alternative, the time dependent DFT (TD-DFT) approach was also tested with both B3LYP and PBE0 functionals. The methodology we proposed shows a comparable or better accuracy with respect to TD-DFT, although the TD-DFT approach with the PBE0 functional is suggested as a suitable estimate for species with the most negative EAs (ca.-2.5 to -3.5 eV), for which stabilization strategies can hardly reach the valence state. As an application, a pool of 8 compounds of key biological interest with EAs which remain unknown or unclear were predicted using the new methodology.

Solvent extraction of irradiated neptunium targets. I. Valence stabilization

International Nuclear Information System (INIS)

Thompson, G.H.; Thompson, M.C.

1977-01-01

Solvent extraction of 237 Np and 238 Pu from irradiated neptunium is being investigated as a possible replacement for the currently used anion exchange process at the Savannah River Plant. Solvent extraction would reduce separations costs and waste volume and increase the production rate. The major difficulty in solvent extraction processing is maintaining neptunium and plutonium in the extractable IV or VI valence states during initial extraction. This study investigated the stability of these states. Results show that: The extractable M(IV) valence states of neptunium and plutonium are mutually unstable in plant dissolver solution (2 g/l 237 Np, 0.4 g/l 238 Pu, 1.2M Al 3+ , 4.6M NO 3 - , and 1M H + ). The reaction rates producing inextractable species from extractable M(IV) or M(VI) are fast enough that greater than or equal to 99.9 percent extractable species in 237 Np-- 238 Pu mixtures cannot be maintained for a practicable processing period

Theory of Valence Transitions in Ytterbium and Europium Intermetallics

International Nuclear Information System (INIS)

Zlatic, V.; Freericks, J.K.

2001-01-01

The exact solution of the multi-component Falicov-Kimball model in infinite-dimensions is presented and used to discuss a new fixed point of valence fluctuating intermetallics with Yb and Eu ions. In these compounds, temperature, external magnetic field, pressure, or chemical pressure induce a transition between a metallic state with the f-ions in a mixed-valent (non-magnetic) configuration and a semi-metallic state with the f-ions in an integral-valence (paramagnetic) configuration. The zero-field transition occurs at the temperature T V , while the zero-temperature transition sets in at the critical field H c . We present the thermodynamic and dynamic properties of the model for an arbitrary concentration of d- and f -electrons. For large U, we find a MI transition, triggered by the temperature or field- induced change in the f-occupancy. (author)

NEVER forget: negative emotional valence enhances recapitulation.

Science.gov (United States)

Bowen, Holly J; Kark, Sarah M; Kensinger, Elizabeth A

2017-07-10

A hallmark feature of episodic memory is that of "mental time travel," whereby an individual feels they have returned to a prior moment in time. Cognitive and behavioral neuroscience methods have revealed a neurobiological counterpart: Successful retrieval often is associated with reactivation of a prior brain state. We review the emerging literature on memory reactivation and recapitulation, and we describe evidence for the effects of emotion on these processes. Based on this review, we propose a new model: Negative Emotional Valence Enhances Recapitulation (NEVER). This model diverges from existing models of emotional memory in three key ways. First, it underscores the effects of emotion during retrieval. Second, it stresses the importance of sensory processing to emotional memory. Third, it emphasizes how emotional valence - whether an event is negative or positive - affects the way that information is remembered. The model specifically proposes that, as compared to positive events, negative events both trigger increased encoding of sensory detail and elicit a closer resemblance between the sensory encoding signature and the sensory retrieval signature. The model also proposes that negative valence enhances the reactivation and storage of sensory details over offline periods, leading to a greater divergence between the sensory recapitulation of negative and positive memories over time. Importantly, the model proposes that these valence-based differences occur even when events are equated for arousal, thus rendering an exclusively arousal-based theory of emotional memory insufficient. We conclude by discussing implications of the model and suggesting directions for future research to test the tenets of the model.

Valence-bond theory of linear Hubbard and Pariser-Parr-Pople models

Science.gov (United States)

Soos, Z. G.; Ramasesha, S.

1984-05-01

The ground and low-lying states of finite quantum-cell models with one state per site are obtained exactly through a real-space basis of valence-bond (VB) diagrams that explicitly conserve the total spin. Regular and alternating Hubbard and Pariser-Parr-Pople (PPP) chains and rings with Ne electrons on N(PPP models, but differ from mean-field results. Molecular PPP parameters describe well the excitations of finite polyenes, odd polyene ions, linear cyanine dyes, and slightly overestimate the absorption peaks in polyacetylene (CH)x. Molecular correlations contrast sharply with uncorrelated descriptions of topological solitons, which are modeled by regular polyene radicals and their ions for both wide and narrow alternation crossovers. Neutral solitons have no midgap absorption and negative spin densities, while the intensity of the in-gap excitation of charged solitons is not enhanced. The properties of correlated states in quantum-cell models with one valence state per site are discussed in the adiabatic limit for excited-state geometries and instabilities to dimerization.

Kekulé-based Valence Bond Model.I. The Ground-state Properties of Conjugated π-Systems

Institute of Scientific and Technical Information of China (English)

LI,Shu-Hua(黎书华); MA,Jing(马晶); JIANG,Yuan-Sheng(江元生)

2002-01-01

The Kekulé-based valence bond ( VB ) method, in which the VB model is solved using covalent Kekulé structures as basis functions, is justified in the present work. This method is dimonstrated to provide satisfactory descriptions for resoance energies and bond ang lengths of benzenoid hydrocarbons, being in good agreement with SCF-MO and experimental results. In additicn, an alternative way of discyssing characters of localizedsubstructures within a polyclic benzenoid system is suggested based upon such sunokufied VB calculations. Finally,the symmetries of VB ground states for nonalternant conjugated systems are also illustrated to be obtainable through these calculations, presenting very useful information for understanding the chemical behaviors of some nonalternant conjugated molecules.

Lie algebraic approach to valence bond theory of π-electron systems: a preliminary study of excited states

Science.gov (United States)

Paldus, J.; Li, X.

1992-10-01

Following a brief outline of various developments and exploitations of the unitary group approach (UGA), and its extension referred to as Clifford algebra UGA (CAUGA), in molecular electronic structure calculations, we present a summary of a recently introduced implementation of CAUGA for the valence bond (VB) method based on the Pariser-Parr-Pople (PPP)-type Hamiltonian. The existing applications of this PPP-VB approach have been limited to groundstates of various π-electron systems or, at any rate, to the lowest states of a given multiplicity. In this paper the method is applied to the low-lying excited states of several archetypal models, namely cyclobutadiene and benzene, representing antiaromatic and aromatic systems, hexatriene, representing linear polyenic systems and, finally, naphthalene, representing polyacenes.

Simultaneous conditioning of valence and arousal.

Science.gov (United States)

Gawronski, Bertram; Mitchell, Derek G V

2014-01-01

Evaluative conditioning (EC) refers to the change in the valence of a conditioned stimulus (CS) due to its pairing with a positive or negative unconditioned stimulus (US). To the extent that core affect can be characterised by the two dimensions of valence and arousal, EC has important implications for the origin of affective responses. However, the distinction between valence and arousal is rarely considered in research on EC or conditioned responses more generally. Measuring the subjective feelings elicited by a CS, the results from two experiments showed that (1) repeated pairings of a CS with a positive or negative US of either high or low arousal led to corresponding changes in both CS valence and CS arousal, (2) changes in CS arousal, but not changes in CS valence, were significantly related to recollective memory for CS-US pairings, (3) subsequent presentations of the CS without the US reduced the conditioned valence of the CS, with conditioned arousal being less susceptible to extinction and (4) EC effects were stronger for high arousal than low arousal USs. The results indicate that the conditioning of affective responses can occur simultaneously along two independent dimensions, supporting evidence in related areas that calls for a consideration of both valence and arousal. Implications for research on EC and the acquisition of emotional dispositions are discussed.

Valence change detection in memristive oxide based heterostructure cells by hard X-ray photoelectron emission spectroscopy

Science.gov (United States)

Kindsmüller, A.; Schmitz, C.; Wiemann, C.; Skaja, K.; Wouters, D. J.; Waser, R.; Schneider, C. M.; Dittmann, R.

2018-04-01

The switching mechanism of valence change resistive memory devices is widely accepted to be an ionic movement of oxygen vacancies resulting in a valence change of the metal cations. However, direct experimental proofs of valence changes in memristive devices are scarce. In this work, we have employed hard X-ray photoelectron emission microscopy (PEEM) to probe local valence changes in Pt/ZrOx/Ta memristive devices. The use of hard X-ray radiation increases the information depth, thus providing chemical information from buried layers. By extracting X-ray photoelectron spectra from different locations in the PEEM images, we show that zirconia in the active device area is reduced compared to a neighbouring region, confirming the valence change in the ZrOx film during electroforming. Furthermore, we succeeded in measuring the Ta 4f spectrum for two different resistance states on the same device. In both states, as well as outside the device region, the Ta electrode is composed of different suboxides without any metallic contribution, hinting to the formation of TaOx during the deposition of the Ta thin film. We observed a reduction of the Ta oxidation state in the low resistance state with respect to the high resistive state. This observation is contradictory to the established model, as the internal redistribution of oxygen between ZrOx and the Ta electrode during switching would lead to an oxidation of the Ta layer in the low resistance state. Instead, we have to conclude that the Ta electrode takes an active part in the switching process in our devices and that oxygen is released and reincorporated in the ZrOx/TaOx bilayer during switching. This is confirmed by the degradation of the high resistance state during endurance measurements under vacuum.

In situ Raman study of redox state changes of mitochondrial cytochromes in a perfused rat heart

DEFF Research Database (Denmark)

Brazhe, Nadezda; Treiman, Marek; Faricelli, Barbara

2013-01-01

We developed a Raman spectroscopy-based approach for simultaneous study of redox changes in c-and b-type cytochromes and for a semiquantitative estimation of the amount of oxygenated myoglobin in a perfused rat heart. Excitation at 532 nm was used to obtain Raman scattering of the myocardial...... surface of the isolated heart at normal and hypoxic conditions. Raman spectra of the heart under normal pO2 demonstrate unique peaks attributable to reduced c-and b-type cytochromes and oxymyoglobin (oMb). The cytochrome peaks decreased in intensity upon FCCP treatment, as predicted from uncoupling...

The power of emotional valence-from cognitive to affective processes in reading.

Science.gov (United States)

Altmann, Ulrike; Bohrn, Isabel C; Lubrich, Oliver; Menninghaus, Winfried; Jacobs, Arthur M

2012-01-01

The comprehension of stories requires the reader to imagine the cognitive and affective states of the characters. The content of many stories is unpleasant, as they often deal with conflict, disturbance or crisis. Nevertheless, unpleasant stories can be liked and enjoyed. In this fMRI study, we used a parametric approach to examine (1) the capacity of increasing negative valence of story contents to activate the mentalizing network (cognitive and affective theory of mind, ToM), and (2) the neural substrate of liking negatively valenced narratives. A set of 80 short narratives was compiled, ranging from neutral to negative emotional valence. For each story mean rating values on valence and liking were obtained from a group of 32 participants in a prestudy, and later included as parametric regressors in the fMRI analysis. Another group of 24 participants passively read the narratives in a three Tesla MRI scanner. Results revealed a stronger engagement of affective ToM-related brain areas with increasingly negative story valence. Stories that were unpleasant, but simultaneously liked, engaged the medial prefrontal cortex (mPFC), which might reflect the moral exploration of the story content. Further analysis showed that the more the mPFC becomes engaged during the reading of negatively valenced stories, the more coactivation can be observed in other brain areas related to the neural processing of affective ToM and empathy.

Cytochrome cbb3 of Thioalkalivibrio is a Na+-pumping cytochrome oxidase

NARCIS (Netherlands)

Muntyan, M.S.; Cherepanov, D.A.; Malinen, A.M.; Bloch, D.A.; Sorokin, D.Y.; Severina, I.I.; Ivashina, T.V.; Lahti, R.; Muyzer, G.; Skulachev, V.P.

2015-01-01

Cytochrome c oxidases (Coxs) are the basic energy transducers in the respiratory chain of the majority of aerobic organisms. Coxs studied to date are redox-driven proton-pumping enzymes belonging to one of three subfamilies: A-, B-, and C-type oxidases. The C-type oxidases (cbb3 cytochromes), which

Crossover and valence band Kβ X-rays of chromium oxides

International Nuclear Information System (INIS)

Fazinic, Stjepko; Mandic, Luka; Kavcic, Matjaz; Bozicevic, Iva

2011-01-01

Kβ X-ray spectra of chromium metal and selected chromium oxides were measured twice using medium resolution flat crystal spectrometer and high resolution spectrometer employing Johansson geometry after excitation with 2 MeV proton beams. The positions and intensities of crossover (Kβ'') and valence (Kβ 2,5 ) band X-rays relative to the primary Kβ X-ray components were extracted in a consistent way. The results were compared with the existing data obtained by proton and photon induced ionization mechanisms and theoretical predictions. The obtained results in peak relative positions and intensities were analyzed in order to study dependence on the chromium oxidation states and chromium-oxygen bond lengths in selected chromium oxides. Our results obtained by both spectrometers confirm that the linear trend observed for the valence peak relative energy shift as a function of chromium oxidation number does not depend on the experimental resolution. Experimental results for normalized intensities (i.e. relative intensities divided with the number of chromium-oxygen pairs) of crossover and valence band X-rays obtained by both spectrometers are in very good agreement, and follow exponential relationship with the average Cr-O bond lengths in corresponding chromium oxides. The observed trends in crossover and valence X-rays normalized intensities could be used to measure the average chromium-oxygen bond length in various chromium oxides, with the sum of both crossover and valence X-ray normalized intensities being the most sensitive measure.

Voice and Valency in San Luis Potosi Huasteco

Science.gov (United States)

Munoz Ledo Yanez, Veronica

2014-01-01

This thesis presents an analysis of the system of transitivity, voice and valency alternations in Huasteco of San Luis Potosi (Mayan) within a functional-typological framework. The study is based on spoken discourse and elicited data collected in the municipalities of Aquismon and Tancanhuitz de Santos in the state of San Luis Potosi, Mexico. The…

Paramagnetic properties of the low- and high-spin states of yeast cytochrome c peroxidase

International Nuclear Information System (INIS)

Vanwetswinkel, Sophie; Nuland, Nico A. J. van; Volkov, Alexander N.

2013-01-01

Here we describe paramagnetic NMR analysis of the low- and high-spin forms of yeast cytochrome c peroxidase (CcP), a 34 kDa heme enzyme involved in hydroperoxide reduction in mitochondria. Starting from the assigned NMR spectra of a low-spin CN-bound CcP and using a strategy based on paramagnetic pseudocontact shifts, we have obtained backbone resonance assignments for the diamagnetic, iron-free protein and the high-spin, resting-state enzyme. The derived chemical shifts were further used to determine low- and high-spin magnetic susceptibility tensors and the zero-field splitting constant (D) for the high-spin CcP. The D value indicates that the latter contains a hexacoordinate heme species with a weak field ligand, such as water, in the axial position. Being one of the very few high-spin heme proteins analyzed in this fashion, the resting state CcP expands our knowledge of the heme coordination chemistry in biological systems

Paramagnetic properties of the low- and high-spin states of yeast cytochrome c peroxidase

Energy Technology Data Exchange (ETDEWEB)

Vanwetswinkel, Sophie; Nuland, Nico A. J. van; Volkov, Alexander N., E-mail: ovolkov@vub.ac.be [Vrije Universiteit Brussel, Jean Jeener NMR Centre, Structural Biology Brussels (Belgium)

2013-09-15

Here we describe paramagnetic NMR analysis of the low- and high-spin forms of yeast cytochrome c peroxidase (CcP), a 34 kDa heme enzyme involved in hydroperoxide reduction in mitochondria. Starting from the assigned NMR spectra of a low-spin CN-bound CcP and using a strategy based on paramagnetic pseudocontact shifts, we have obtained backbone resonance assignments for the diamagnetic, iron-free protein and the high-spin, resting-state enzyme. The derived chemical shifts were further used to determine low- and high-spin magnetic susceptibility tensors and the zero-field splitting constant (D) for the high-spin CcP. The D value indicates that the latter contains a hexacoordinate heme species with a weak field ligand, such as water, in the axial position. Being one of the very few high-spin heme proteins analyzed in this fashion, the resting state CcP expands our knowledge of the heme coordination chemistry in biological systems.

Adjustment of valence state of Pu and Np in nitric solution containing N,N-dimethylhydroxylamine and monomethylhydrazine by electrolysis

Energy Technology Data Exchange (ETDEWEB)

Zhang, H.; Ye, G.A.; Cong, H.F. [China Institute of Atomic Energy, Beijing (China)] [and others

2012-07-01

A study of the electrochemical behaviors of N,N-dimethylhydroxylamine (DMHAN) and monomethyl hydrazine (MMH) in nitric acid solution on Pt electrodes were carried out by cyclic voltammetry (CV) and linear sweep voltammetry (LSV) methods. The diffusion coefficients of DMHAN and MMH were obtained by CV. The values are found to be 0.53 x 10{sup -6}6 cm{sup 2}/s D{sub (DMHAN)} and 0.88 x 10{sup -5} cm{sup 2}/s D{sub (MMH)}. The equilibrium potentials (+0.47 V vs. SCE for DMHAN and +0.31 V vs. SCE for MMH) were also measured using Tafel curves. Various valence states of Pu and Np in HNO{sub 3} solution containing DMHAN and MMH in the electrolytic process were investigated by an electrolytic cell using a platinum as the anode and a titanium plate as the cathode. In this procedure, MMH was first electro-oxidized on the Pt anode and Np(V) was reduced to Np(IV) on the Ti cathode. After MMH was entirely consumed, the accumulation of HNO{sub 2} (due to the electrochemical reduction of nitric acid on the Ti cathode) caused a significantly fast catalytic reaction of DMHAN with HNO{sub 3} to form HNO{sub 2}. HNO{sub 2} can oxidize Pu(III) to Pu(IV) quickly. As a result, both oxidation states of Pu and Np were found to be tetravalent in the post-electrolysis solution. A convenient method to keep the post-electrolysis solution at 70 C was used to adjust the oxidation state of Np in it's pentavalent state while retaining the tetravalent state of Pu. This study developed an electrolytic process for the preparation of 2AF feed (the feed of Pu purification cycle) in APOR (Advanced Purex Process Based on Organic Reductants) process by electrochemically oxidizing Pu(III) and selectively adjusting the valence state of neptunium to either Np(IV) or Np(V). (orig.)

Intermediate valence spectroscopy

International Nuclear Information System (INIS)

Gunnarsson, O.; Schoenhammer, K.

1987-01-01

Spectroscopic properties of intermediate valence compounds are studied using the Anderson model. Due to the large orbital and spin degeneracy N/sub f/ of the 4f-level, 1/N/sub f/ can be treated as a small parameter. This approach provides exact T = 0 results for the Anderson impurity model in the limit N/sub f/ → ∞, and by adding 1/N/sub f/ corrections some properties can be calculated accurately even for N/sub f/ = 1 or 2. In particular valence photoemission and resonance photoemission spectroscopies are studied. A comparison of theoretical and experimental spectra provides an estimate of the parameters in the model. Core level photoemission spectra provide estimates of the coupling between the f-level and the conduction states and of the f-level occupancy. With these parameters the model gives a fair description of other electron spectroscopies. For typical parameters the model predicts two structures in the f-spectrum, namely one structure at the f-level and one at the Fermi energy. The resonance photoemission calculation gives a photon energy dependence for these two peaks in fair agreement with experiment. The peak at the Fermi energy is partly due to a narrow Kondo resonance, resulting from many-body effects and the presence of a continuous, partly filled conduction band. This resonance is related to a large density of low-lying excitations, which explains the large susceptibility and specific heat observed for these systems at low temperatures. 38 references, 11 figures, 2 tables

Antimycin-insensitive mutants of Candida utilis II. The effects of antimycin on Cytochrome b

DEFF Research Database (Denmark)

Grimmelikhuijzen, C J; Marres, C A; Slater, Conor

1975-01-01

1. Cytochrome b-562 is more reduced in submitochondrial particles of mutant 28 during the aerobic steady-state respiration with succinate than in particles of the wild type. When anaerobiosis is reached, the reduction of cytochrome b is preceded by a rapid reoxidation in the mutnat. A similar reo...

Human Amygdala Represents the Complete Spectrum of Subjective Valence

Science.gov (United States)

Jin, Jingwen; Zelano, Christina; Gottfried, Jay A.

2015-01-01

Although the amygdala is a major locus for hedonic processing, how it encodes valence information is poorly understood. Given the hedonic potency of odor stimuli and the amygdala's anatomical proximity to the peripheral olfactory system, we combined high-resolution fMRI with pattern-based multivariate techniques to examine how valence information is encoded in the amygdala. Ten human subjects underwent fMRI scanning while smelling 9 odorants that systematically varied in perceived valence. Representational similarity analyses showed that amygdala codes the entire dimension of valence, ranging from pleasantness to unpleasantness. This unidimensional representation significantly correlated with self-reported valence ratings but not with intensity ratings. Furthermore, within-trial valence representations evolved over time, prioritizing earlier differentiation of unpleasant stimuli. Together, these findings underscore the idea that both spatial and temporal features uniquely encode pleasant and unpleasant odor valence in the amygdala. The availability of a unidimensional valence code in the amygdala, distributed in both space and time, would create greater flexibility in determining the pleasantness or unpleasantness of stimuli, providing a mechanism by which expectation, context, attention, and learning could influence affective boundaries for guiding behavior. SIGNIFICANCE STATEMENT Our findings elucidate the mechanisms of affective processing in the amygdala by demonstrating that this brain region represents the entire valence dimension from pleasant to unpleasant. An important implication of this unidimensional valence code is that pleasant and unpleasant valence cannot coexist in the amygdale because overlap of fMRI ensemble patterns for these two valence extremes obscures their unique content. This functional architecture, whereby subjective valence maps onto a pattern continuum between pleasant and unpleasant poles, offers a robust mechanism by which context

Atomic contributions to the valence band photoelectron spectra of metal-free, iron and manganese phthalocyanines

Energy Technology Data Exchange (ETDEWEB)

Bidermane, I., E-mail: ieva.bidermane@physics.uu.se [Department of Physics and Astronomy, Uppsala University, Box-516, 75120 Uppsala (Sweden); Institut des Nanosciences de Paris, UPMC Univ. Paris 06, CNRS UMR 7588, F-75005 Paris (France); Brumboiu, I.E. [Department of Physics and Astronomy, Uppsala University, Box-516, 75120 Uppsala (Sweden); Totani, R. [Department of Physical and Chemical Sciences, University of L’Aquila, Via Vetoio, Coppito, I-67010 L’Aquila (Italy); Grazioli, C. [CNR-IOM, Laboratorio TASC, ss. 14 km. 163.5, Basovizza, 34149 Trieste (Italy); Departement of Chemical and Pharmaceutical Sciences, University of Trieste (Italy); Shariati-Nilsson, M.N.; Herper, H.C.; Eriksson, O.; Sanyal, B. [Department of Physics and Astronomy, Uppsala University, Box-516, 75120 Uppsala (Sweden); Ressel, B. [University of Nova Gorica, Vipavska Cesta 11c, 5270 Ajdovščina (Slovenia); Simone, M. de [CNR-IOM, Laboratorio TASC, ss. 14 km. 163.5, Basovizza, 34149 Trieste (Italy); Lozzi, L. [Department of Physical and Chemical Sciences, University of L’Aquila, Via Vetoio, Coppito, I-67010 L’Aquila (Italy); Brena, B.; Puglia, C. [Department of Physics and Astronomy, Uppsala University, Box-516, 75120 Uppsala (Sweden)

2015-11-15

Highlights: • In detail comparison between the valence band structure of H{sub 2}Pc, FePc and MnPc. • Comparison between the gas phase samples and thin evaporated films on Au (1 1 1). • Detailed analysis of the atomic orbital contributions to the valence band features. • DFT/HSE06 study of the valence band electronic structure of H{sub 2}Pc, FePc and MnPc. - Abstract: The present work reports a photoelectron spectroscopy study of the low-energy region of the valence band of metal-free phthalocyanine (H{sub 2}Pc) compared with those of iron phthalocyanine (FePc) and manganese phthalocyanine (MnPc). We have analysed in detail the atomic orbital composition of the valence band both experimentally, by making use of the variation in photoionization cross-sections with photon energy, and theoretically, by means of density functional theory. The atomic character of the Highest Occupied Molecular Orbital (HOMO), reflected on the outermost valence band binding energy region, is different for MnPc as compared to the other two molecules. The peaks related to the C 2p contributions, result in the HOMO for H{sub 2}Pc and FePc and in the HOMO-1 for MnPc as described by the theoretical predictions, in very good agreement with the experimental results. The DFT simulations, discerning the atomic contribution to the density of states, indicate how the central metal atom interacts with the C and N atoms of the molecule, giving rise to different partial and total density of states for these three Pc molecules.

Thermal recombination: Beyond the valence quark approximation

Energy Technology Data Exchange (ETDEWEB)

Mueller, B. [Department of Physics, Duke University, Durham, NC 27708 (United States); Fries, R.J. [School of Physics and Astronomy, University of Minnesota, Minneapolis, MN 55455 (United States)]. E-mail: fries@physics.umn.edu; Bass, S.A. [Department of Physics, Duke University, Durham, NC 27708 (United States); RIKEN BNL Research Center, Brookhaven National Laboratory, Upton, NY 11973 (United States)

2005-07-07

Quark counting rules derived from recombination models agree well with data on hadron production at intermediate transverse momenta in relativistic heavy-ion collisions. They convey a simple picture of hadrons consisting only of valence quarks. We discuss the inclusion of higher Fock states that add sea quarks and gluons to the hadron structure. We show that, when recombination occurs from a thermal medium, hadron spectra remain unaffected by the inclusion of higher Fock states. However, the quark number scaling for elliptic flow is somewhat affected. We discuss the implications for our understanding of data from the Relativistic Heavy Ion Collider.

Consistent gaussian basis sets of double- and triple-zeta valence with polarization quality of the fifth period for solid-state calculations.

Science.gov (United States)

Laun, Joachim; Vilela Oliveira, Daniel; Bredow, Thomas

2018-02-22

Consistent basis sets of double- and triple-zeta valence with polarization quality for the fifth period have been derived for periodic quantum-chemical solid-state calculations with the crystalline-orbital program CRYSTAL. They are an extension of the pob-TZVP basis sets, and are based on the full-relativistic effective core potentials (ECPs) of the Stuttgart/Cologne group and on the def2-SVP and def2-TZVP valence basis of the Ahlrichs group. We optimized orbital exponents and contraction coefficients to supply robust and stable self-consistent field (SCF) convergence for a wide range of different compounds. The computed crystal structures are compared to those obtained with standard basis sets available from the CRYSTAL basis set database. For the applied hybrid density functional PW1PW, the average deviations of calculated lattice constants from experimental references are smaller with pob-DZVP and pob-TZVP than with standard basis sets. © 2018 Wiley Periodicals, Inc. © 2018 Wiley Periodicals, Inc.

Deduction of the chemical state and the electronic structure of Nd{sub 2}Fe{sub 14}B compound from X-ray photoelectron spectroscopy core-level and valence-band spectra

Energy Technology Data Exchange (ETDEWEB)

Wang, Jing; Liang, Le [School of Materials Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240 (China); Zhang, Lanting, E-mail: lantingzh@sjtu.edu.cn, E-mail: lmsun@sjtu.edu.cn [School of Materials Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240 (China); Hirano Institute for Materials Innovation, Shanghai Jiao Tong University, Shanghai 200240 (China); Sun, Limin, E-mail: lantingzh@sjtu.edu.cn, E-mail: lmsun@sjtu.edu.cn [Instrumental Analysis Center, Shanghai Jiao Tong University, Shanghai 200240 (China); Hirano, Shinichi [Hirano Institute for Materials Innovation, Shanghai Jiao Tong University, Shanghai 200240 (China)

2014-10-28

Characterization of chemical state and electronic structure of the technologically important Nd{sub 2}Fe{sub 14}B compound is attractive for understanding the physical nature of its excellent magnetic properties. X-ray photoelectron spectroscopy (XPS) study of such rare-earth compound is important and also challenging due to the easy oxidation of surface and small photoelectron cross-sections of rare-earth 4f electrons and B 2p electrons, etc. Here, we reported an investigation based on XPS spectra of Nd{sub 2}Fe{sub 14}B compound as a function of Ar ion sputtering time. The chemical state of Fe and that of B in Nd{sub 2}Fe{sub 14}B compound can be clearly determined to be 0 and −3, respectively. The Nd in Nd{sub 2}Fe{sub 14}B compound is found to have the chemical state of close to +3 instead of +3 as compared with the Nd in Nd{sub 2}O{sub 3}. In addition, by comparing the valence-band spectrum of Nd{sub 2}Fe{sub 14}B compound to that of the pure Fe, the contributions from Nd, Fe, and B to the valence-band structure of Nd{sub 2}Fe{sub 14}B compound is made more clear. The B 2p states and B 2s states are identified to be at ∼11.2 eV and ∼24.6 eV, respectively, which is reported for the first time. The contribution from Nd 4f states can be identified both in XPS core-level spectrum and XPS valence-band spectrum. Although Nd 4f states partially hybridize with Fe 3d states, Nd 4f states are mainly localized in Nd{sub 2}Fe{sub 14}B compound.

A study of the valence shell spectroscopic and thermodynamic properties of trifluoronitrosomethane cations

International Nuclear Information System (INIS)

Graham, D.M.; Powis, I.; Underwood, J.G.; Shaw, D.A.; Holland, D.M.P.

2012-01-01

Highlights: ► Fragmentation processes in CF 3 NO have been studied using mass spectrometry. ► Singly charged atomic fragments have been observed. ► Experimental appearance energies have been compared to thermochemical estimates. ► Hartree Fock transition energies and oscillator strengths have been calculated. - Abstract: A time-of-flight mass spectrometry study has been carried out to investigate the fragmentation processes occurring in trifluoronitrosomethane (CF 3 NO) as a result of valence shell photoionisation. Synchrotron radiation has been used to record spectra in the photon energy range ∼10–42 eV, and appearance energies have been determined for 10 fragment ions. At high excitation energies, singly charged atomic fragments have been observed. For the main dissociation channels, leading to the formation of NO + , CF 2 + or CF 3 + , the experimental appearance energies have been compared with thermochemical estimates, and a satisfactory agreement has been found. Structure observed in the total ion yield curve has been interpreted with the aid of excited state transition energies and oscillator strengths obtained in a time-dependent Hartree Fock calculation. The theoretical results show that configuration interaction strongly affects many of the valence states. A HeI excited photoelectron spectrum of CF 3 NO has been measured and the orbital ionisation energies have been compared with theoretical values computed using the Outer Valence Green’s Function approach. A large Franck–Condon gap is observed between the 12a′ (n - ) and the 11a ′ state bands, in accord with the calculated vertical ionisation energies of 10.87 and 16.32 eV for the 12a′ (n − ) and the 11a′ (n + ) orbitals, respectively. In the ion yield curve, the corresponding energy range is strongly influenced by autoionising valence states.

Emotional valence and the free-energy principle.

Science.gov (United States)

Joffily, Mateus; Coricelli, Giorgio

2013-01-01

The free-energy principle has recently been proposed as a unified Bayesian account of perception, learning and action. Despite the inextricable link between emotion and cognition, emotion has not yet been formulated under this framework. A core concept that permeates many perspectives on emotion is valence, which broadly refers to the positive and negative character of emotion or some of its aspects. In the present paper, we propose a definition of emotional valence in terms of the negative rate of change of free-energy over time. If the second time-derivative of free-energy is taken into account, the dynamics of basic forms of emotion such as happiness, unhappiness, hope, fear, disappointment and relief can be explained. In this formulation, an important function of emotional valence turns out to regulate the learning rate of the causes of sensory inputs. When sensations increasingly violate the agent's expectations, valence is negative and increases the learning rate. Conversely, when sensations increasingly fulfil the agent's expectations, valence is positive and decreases the learning rate. This dynamic interaction between emotional valence and learning rate highlights the crucial role played by emotions in biological agents' adaptation to unexpected changes in their world.

Emotional valence and the free-energy principle.

Directory of Open Access Journals (Sweden)

Mateus Joffily

Full Text Available The free-energy principle has recently been proposed as a unified Bayesian account of perception, learning and action. Despite the inextricable link between emotion and cognition, emotion has not yet been formulated under this framework. A core concept that permeates many perspectives on emotion is valence, which broadly refers to the positive and negative character of emotion or some of its aspects. In the present paper, we propose a definition of emotional valence in terms of the negative rate of change of free-energy over time. If the second time-derivative of free-energy is taken into account, the dynamics of basic forms of emotion such as happiness, unhappiness, hope, fear, disappointment and relief can be explained. In this formulation, an important function of emotional valence turns out to regulate the learning rate of the causes of sensory inputs. When sensations increasingly violate the agent's expectations, valence is negative and increases the learning rate. Conversely, when sensations increasingly fulfil the agent's expectations, valence is positive and decreases the learning rate. This dynamic interaction between emotional valence and learning rate highlights the crucial role played by emotions in biological agents' adaptation to unexpected changes in their world.

Valence behavior of Eu-ions in intermetallic compound Ce{sub 0.5}Eu{sub 0.5}Pd{sub 3}B{sub 0.5}

Energy Technology Data Exchange (ETDEWEB)

Pandey, Abhishek, E-mail: apandey@ameslab.gov [Experimental Condensed Matter Physics Division, Saha Institute of Nuclear Physics, 1/AF, Bidhannagar, Kolkata 700064 (India); S.N. Bose National Centre for Basic Sciences, Block-JD, Sector-III, Salt Lake, Kolkata 700098 (India); Mazumdar, Chandan, E-mail: chandan.mazumdar@saha.ac.in [S.N. Bose National Centre for Basic Sciences, Block-JD, Sector-III, Salt Lake, Kolkata 700098 (India); Ranganathan, R. [S.N. Bose National Centre for Basic Sciences, Block-JD, Sector-III, Salt Lake, Kolkata 700098 (India); Raghavendra Reddy, V.; Gupta, Ajay [UGC-DAE Consortium for Scientific Research, University Campus, Khandawa Road, Indore (India)

2011-12-15

We have studied the valence behavior of rare-earth ions, in particular Eu-ions, in a cubic intermetallic compound Ce{sub 0.5}Eu{sub 0.5}Pd{sub 3}B{sub 0.5} which is a homogeneous solid solution of two mixed-valent compounds CePd{sub 3} and EuPd{sub 3}B. Results of {sup 151}Eu Moessbauer spectroscopic measurements show that two different valence states, i.e., divalent- and trivalent-like states of Eu-ions exist in the compound. The possible reason for the observed heterogeneous valency vis-a-vis the variation in the chemical environment and the number of nearest-neighbor B atoms surrounding the Eu-ions has been discussed. Our results demonstrate that B incorporation in such Eu-based cubic intermetallic compounds leads to a situation where heterogeneous-valence state of Eu-ions is an energetically favorable ground state. - Highlights: > Intermetallic compound Ce{sub 0.5}Eu{sub 0.5}Pd{sub 3}B{sub 0.5} crystallizes in a single phase. > Eu-ions in Ce{sub 0.5}Eu{sub 0.5}Pd{sub 3}B{sub 0.5} are charge-ordered compared to +2.3 valency in Ce{sub 0.5}Eu{sub 0.5}Pd{sub 3}. > B incorporation makes charge-ordered state of Eu-ions energetically more favorable. > Nearest-neighbor chemical environment affects the Eu valency.

Ab initio valence calculations in chemistry

CERN Document Server

Cook, D B

1974-01-01

Ab Initio Valence Calculations in Chemistry describes the theory and practice of ab initio valence calculations in chemistry and applies the ideas to a specific example, linear BeH2. Topics covered include the Schrödinger equation and the orbital approximation to atomic orbitals; molecular orbital and valence bond methods; practical molecular wave functions; and molecular integrals. Open shell systems, molecular symmetry, and localized descriptions of electronic structure are also discussed. This book is comprised of 13 chapters and begins by introducing the reader to the use of the Schrödinge

Quantum computational capability of a 2D valence bond solid phase

International Nuclear Information System (INIS)

Miyake, Akimasa

2011-01-01

Highlights: → Our model is the 2D valence bond solid phase of a quantum antiferromagnet. → Universal quantum computation is processed by measurements of quantum correlations. → An intrinsic complexity of strongly-correlated quantum systems could be a resource. - Abstract: Quantum phases of naturally-occurring systems exhibit distinctive collective phenomena as manifestation of their many-body correlations, in contrast to our persistent technological challenge to engineer at will such strong correlations artificially. Here we show theoretically that quantum correlations exhibited in the 2D valence bond solid phase of a quantum antiferromagnet, modeled by Affleck, Kennedy, Lieb, and Tasaki (AKLT) as a precursor of spin liquids and topological orders, are sufficiently complex yet structured enough to simulate universal quantum computation when every single spin can be measured individually. This unveils that an intrinsic complexity of naturally-occurring 2D quantum systems-which has been a long-standing challenge for traditional computers-could be tamed as a computationally valuable resource, even if we are limited not to create newly entanglement during computation. Our constructive protocol leverages a novel way to herald the correlations suitable for deterministic quantum computation through a random sampling, and may be extensible to other ground states of various 2D valence bond phases beyond the AKLT state.

Influence of humic substances and wood decay products on the valency state of uranium

International Nuclear Information System (INIS)

Abraham, A.

2002-01-01

The purpose of the present study was to investigate the influence of dissolved natural substances on the oxidation state of iron and uranium. The ongoing remediation of uranium mining areas in Saxony and Thuringia involves flooding of extended pits, submerging and subjecting to microbial decay considerable amounts of pit timber in the process. This gives rise to the problem whether the reductive environment which develops as a result of wood decay in the pit water is capable of reducing the uranium (VI) and iron (III) contained in the flood water. Measurements of the valency state of uranium and iron following their interaction with natural decay products were performed by means of electrochemical, photometric and laser spectroscopic methods. This was followed by sorption experiments with a view to collecting phenomenological data on the binding behaviour of uranium species with respect to the rock bed of the Western Erz Hills and the sediments of the Elbe valley under different redox potential conditions. The study was concluded with redox potential calculations aimed at describing the state of pit waters as well as characterising analogous natural waters. The study was performed using humic acids for alkaline brown coal extract, high moor humic substances originating from natural microbial wood decay for wood decay products, and products from hydrothermal wood decomposition as well as lignin for a methanolic wood extract [de

Electroencephalography Based Analysis of Working Memory Load and Affective Valence in an N-back Task with Emotional Stimuli.

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Grissmann, Sebastian; Faller, Josef; Scharinger, Christian; Spüler, Martin; Gerjets, Peter

2017-01-01

Most brain-based measures of the electroencephalogram (EEG) are used in highly controlled lab environments and only focus on narrow mental states (e.g., working memory load). However, we assume that outside the lab complex multidimensional mental states are evoked. This could potentially create interference between EEG signatures used for identification of specific mental states. In this study, we aimed to investigate more realistic conditions and therefore induced a combination of working memory load and affective valence to reveal potential interferences in EEG measures. To induce changes in working memory load and affective valence, we used a paradigm which combines an N-back task (for working memory load manipulation) with a standard method to induce affect (affective pictures taken from the International Affective Picture System (IAPS) database). Subjective ratings showed that the experimental task was successful in inducing working memory load as well as affective valence. Additionally, performance measures were analyzed and it was found that behavioral performance decreased with increasing workload as well as negative valence, showing that affective valence can have an effect on cognitive processing. These findings are supported by changes in frontal theta and parietal alpha power, parameters used for measuring of working memory load in the EEG. However, these EEG measures are influenced by the negative valence condition as well and thereby show that detection of working memory load is sensitive to affective contexts. Unexpectedly, we did not find any effects for EEG measures typically used for affective valence detection (Frontal Alpha Asymmetry (FAA)). Therefore we assume that the FAA measure might not be usable if cognitive workload is induced simultaneously. We conclude that future studies should account for potential context-specifity of EEG measures.

Neurons for hunger and thirst transmit a negative-valence teaching signal

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Gong, Rong; Magnus, Christopher J.; Yu, Yang; Sternson, Scott M.

2015-01-01

Homeostasis is a biological principle for regulation of essential physiological parameters within a set range. Behavioural responses due to deviation from homeostasis are critical for survival, but motivational processes engaged by physiological need states are incompletely understood. We examined motivational characteristics and dynamics of two separate neuron populations that regulate energy and fluid homeostasis by using cell type-specific activity manipulations in mice. We found that starvation-sensitive AGRP neurons exhibit properties consistent with a negative-valence teaching signal. Mice avoided activation of AGRP neurons, indicating that AGRP neuron activity has negative valence. AGRP neuron inhibition conditioned preference for flavours and places. Correspondingly, deep-brain calcium imaging revealed that AGRP neuron activity rapidly reduced in response to food-related cues. Complementary experiments activating thirst-promoting neurons also conditioned avoidance. Therefore, these need-sensing neurons condition preference for environmental cues associated with nutrient or water ingestion, which is learned through reduction of negative-valence signals during restoration of homeostasis. PMID:25915020

The role of valence focus and appraisal overlap in emotion differentiation.

Science.gov (United States)

Erbas, Yasemin; Ceulemans, Eva; Koval, Peter; Kuppens, Peter

2015-06-01

Emotion differentiation refers to the level of specificity with which people distinguish between their emotional states and is considered to play an important role for psychological well-being. Yet, not much is known about what characterizes people high or low in emotion differentiation and what underlies these differences. In 2 studies involving experience sampling (Studies 1-2) and lab based (Study 2) methods, we investigated how emotion differentiation is related to individual differences in valence focus and the overlap in appraisal patterns between emotions. In line with expectations, results showed that high levels of both positive and negative emotion differentiation are related to lower levels of valence focus and lower levels of appraisal overlap between emotions. These findings suggest that individuals who are low in emotion differentiation mainly emphasize the valence aspect of emotions while individuals who are high in emotion differentiation make stronger distinctions between emotions in terms of their underlying appraisal profiles. (c) 2015 APA, all rights reserved).

In-silico assessment of protein-protein electron transfer. a case study: cytochrome c peroxidase--cytochrome c.

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Frank H Wallrapp

Full Text Available The fast development of software and hardware is notably helping in closing the gap between macroscopic and microscopic data. Using a novel theoretical strategy combining molecular dynamics simulations, conformational clustering, ab-initio quantum mechanics and electronic coupling calculations, we show how computational methodologies are mature enough to provide accurate atomistic details into the mechanism of electron transfer (ET processes in complex protein systems, known to be a significant challenge. We performed a quantitative study of the ET between Cytochrome c Peroxidase and its redox partner Cytochrome c. Our results confirm the ET mechanism as hole transfer (HT through residues Ala194, Ala193, Gly192 and Trp191 of CcP. Furthermore, our findings indicate the fine evolution of the enzyme to approach an elevated turnover rate of 5.47 × 10(6 s(-1 for the ET between Cytc and CcP through establishment of a localized bridge state in Trp191.

Cytochrome b5 reductase is the component from neuronal synaptic plasma membrane vesicles that generates superoxide anion upon stimulation by cytochrome c

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Alejandro K. Samhan-Arias

2018-05-01

Full Text Available In this work, we measured the effect of cytochrome c on the NADH-dependent superoxide anion production by synaptic plasma membrane vesicles from rat brain. In these membranes, the cytochrome c stimulated NADH-dependent superoxide anion production was inhibited by antibodies against cytochrome b5 reductase linking the production to this enzyme. Measurement of the superoxide anion radical generated by purified recombinant soluble and membrane cytochrome b5 reductase corroborates the production of the radical by different enzyme isoforms. In the presence of cytochrome c, a burst of superoxide anion as well as the reduction of cytochrome c by cytochrome b5 reductase was measured. Complex formation between both proteins suggests that cytochrome b5 reductase is one of the major partners of cytochrome c upon its release from mitochondria to the cytosol during apoptosis. Superoxide anion production and cytochrome c reduction are the consequences of the stimulated NADH consumption by cytochrome b5 reductase upon complex formation with cytochrome c and suggest a major role of this enzyme as an anti-apoptotic protein during cell death.

Production, purification and detergent exchange of isotopically labeled Bacillussubtilis cytochrome b₅₅₈ (SdhC).

Science.gov (United States)

Baureder, Michael; Hederstedt, Lars

2011-11-01

Cytochrome b₅₅₈ of the gram-positive bacterium Bacillussubtilis is the membrane anchor subunit of the succinate:quinone oxidoreductase of the citric acid cycle. The cytochrome consists of the SdhC polypeptide (202 residues) and two protoheme IX groups that function in transmembrane electron transfer to menaquinone. The general structure of the cytochrome is known from extensive experimental studies and by comparison to Wolinellasuccinogenes fumarate reductase for which the X-ray crystal structure has been determined. Solution state NMR can potentially be used to identify the quinone binding site(s) and study, e.g. redox-linked, dynamics of cytochrome b₅₅₈. In this work we present an efficient procedure for the isolation of preparative amounts of isotopically labeled B. subtilis cytochrome b₅₅₈ produced in Escherichia coli. We have also evaluated several detergents suitable for NMR for their effectiveness in maintaining the cytochrome solubilized and intact for days at room temperature. Copyright © 2011 Elsevier Inc. All rights reserved.

Valency and molecular structure

CERN Document Server

Cartmell, E

1977-01-01

Valency and Molecular Structure, Fourth Edition provides a comprehensive historical background and experimental foundations of theories and methods relating to valency and molecular structures. In this edition, the chapter on Bohr theory has been removed while some sections, such as structures of crystalline solids, have been expanded. Details of structures have also been revised and extended using the best available values for bond lengths and bond angles. Recent developments are mostly noted in the chapter on complex compounds, while a new chapter has been added to serve as an introduction t

Calorimetric studies of the thermal denaturation of cytochrome c peroxidase

International Nuclear Information System (INIS)

Kresheck, G.C.; Erman, J.E.

1988-01-01

Two endotherms are observed by differential scanning calorimetry during the thermal denaturation of cytochrome c peroxidase at pH 7.0. The transition midpoint temperatures (t/sub m/) were 43.9 +- 1.4 and 63.3 +- 1.6 0 C, independent of concentration. The two endotherms were observed at all pH values between 4 and 8, with the transition temperatures varying with pH. Precipitation was observed between pH 4 and 6, and only qualitative data are presented for this region. The thermal unfolding of cytochrome c peroxidase was sensitive to the presence and ligation state of the heme. Only a single endotherm was observed for the unfolding of the apoprotein, and this transition was similar to the high-temperature transition in the holoenzyme. Addition of KCN to the holoenzyme increases the midpoint of the high-temperature transition whereas the low-temperature transition was increased upon addition of KF. Binding of the natural substrate ferricytochrome c to the enzyme increases the low-temperature transition by 4.8 +- 1.3 0 C but has no effect on the high-temperature transition at pH 7. The presence of cytochrome c peroxidase decreases the stability of cytochrome c, and both proteins appear to unfold simultaneously. The results are discussed in terms of the two domains evident in the X-ray crystallographic structure of cytochrome c peroxidase

[Emotional valence of words in schizophrenia].

Science.gov (United States)

Jalenques, I; Enjolras, J; Izaute, M

2013-06-01

Emotion recognition is a domain in which deficits have been reported in schizophrenia. A number of emotion classification studies have indicated that emotion processing deficits in schizophrenia are more pronounced for negative affects. Given the difficulty of developing material suitable for the study of these emotional deficits, it would be interesting to examine whether patients suffering from schizophrenia are responsive to positively and negatively charged emotion-related words that could be used within the context of remediation strategies. The emotional perception of words was examined in a clinical experiment involving schizophrenia patients. This emotional perception was expressed by the patients in terms of the valence associated with the words. In the present study, we investigated whether schizophrenia patients would assign the same negative and positive valences to words as healthy individuals. Twenty volunteer, clinically stable, outpatients from the Psychiatric Service of the University Hospital of Clermont-Ferrand were recruited. Diagnoses were based on DSM-IV criteria. Global psychiatric symptoms were assessed using the Positive and Negative Symptoms Scale (PANSS). The patients had to evaluate the emotional valence of a set of 300 words on a 5-point scale ranging from "very unpleasant" to "very pleasant". . The collected results were compared with those obtained by Bonin et al. (2003) [13] from 97 University students. Correlational analyses of the two studies revealed that the emotional valences were highly correlated, i.e. the schizophrenia patients estimated very similar emotional valences. More precisely, it was possible to examine three separate sets of 100 words each (positive words, neutral words and negative words). The positive words that were evaluated were the more positive words from the norms collected by Bonin et al. (2003) [13], and the negative words were the more negative examples taken from these norms. The neutral words

The power of emotional valence – From cognitive to affective processes in reading

Directory of Open Access Journals (Sweden)

Ulrike eAltmann

2012-06-01

Full Text Available The comprehension of stories requires the reader to imagine the cognitive and affective states of the characters. The content of many stories is unpleasant, as they often deal with conflict, disturbance or crisis. Nevertheless, unpleasant stories can be liked and enjoyed. In this fMRI study, we used a parametric approach to examine (1 the capacity of increasing negative valence of story contents to activate the mentalizing network (cognitive and affective theory of mind, ToM, and (2 the neural substrate of liking negatively valenced narratives. A set of 80 short narratives was compiled, ranging from neutral to negative emotional valence. For each story mean rating values on valence and liking were obtained from a group of 32 participants in a prestudy, and later included as parametric regressors in the fMRI analysis. Another group of 24 participants passively read the narratives in a 3 Tesla MRI scanner. Results revealed a stronger engagement of affective ToM-related brain areas with increasingly negative story valence. Stories that were unpleasant, but simulatiously liked, selectively engaged the medial prefrontal cortex (mPFC, which might reflect the moral exploration of the story content. Further analysis showed that the more the mPFC becomes engaged during the reading of negatively valenced stories, the more coactivation can be observed in other brain areas related to the neural processing of affective ToM and empathy.

Valence mixing in YbCuAl: a case study

International Nuclear Information System (INIS)

Mattens, W.

1980-01-01

Results are presented of a study of the valence state of Yb in the intermetallic compound YbCuAl. Both macroscopic physical properties (magnetic susceptibility, heat capacity, thermal expansion, electric resistivity) and microscopic physical properties (neutron inelastic scattering, nuclear magnetic resonance) are determined. The results are compared with a local Fermi liquid theory. (G.T.H.)

Localized description of valence fluctuations

International Nuclear Information System (INIS)

Alascio, B.; Allub, R.; Aligia, A.

1979-07-01

The authors set up a model for intermediate valence equivalent to the ''atomic'' limit of the Anderson Hamiltonian. Detailed analysis of this model shows that most of the essential characteristics of valence fluctuators are already present in this crudely simplified Hamiltonian. The spin-spin and the 4f charge-charge correlation functions are studied and it is shown that it is possible to define a spin fluctuation frequency ωsub(s.f.) and a charge fluctuation frequency ωsub(ch.f.).ωsub(s.f.) and ωsub(ch.f.) can differ considerably for some values of the parameters of the model. The magnetic susceptibility and the specific heat are calculated as functions of temperature and it is shown how the results simulate the behaviour found in valence fluctuators. (author)

Magnetic re-entrance in intermediate valence compounds

International Nuclear Information System (INIS)

Allub, R.; Machiavelli, O.; Balseiro, C.; Alascio, B.

1980-01-01

The possibility is explored of magnetic re-entrance in intermediate valence compounds. Using a simplified Anderson-Lattice model the pressure-temperature magnetic phase diagram is obtained. This diagram shows that for some value of the microscopic parameters the temperature induced two transitions (non-magnetic to magnetically ordered to paramagnetic). The magnetization and the average occupation number of the localized state are calculated. Estimations of the observability of the effect in systems like CeAl 2 are made. (author)

Electronic structure and nature of the ground state of the mixed-valence binuclear tetra(mu-1,8-naphthyridine-N,N')-bis(halogenonickel) tetraphenylborate complexes: experimental and DFT characterization.

Science.gov (United States)

Bencini, Alessandro; Berti, Elisabetta; Caneschi, Andrea; Gatteschi, Dante; Giannasi, Elisa; Invernizzi, Ivana

2002-08-16

The ground state electronic structure of the mixed-valence systems [Ni(2)(napy)(4)X(2)](BPh(4)) (napy=1,8-naphthyridine; X=Cl, Br, I) was studied with combined experimental (X-ray diffraction, temperature dependence of the magnetic susceptibility, and high-field EPR spectroscopy) and theoretical (DFT) methods. The zero-field splitting (zfs) ground S=3/2 spin state is axial with /D/ approximately 3 cm(-1). The iodide derivative was found to be isostructural with the previously reported bromide complex, but not isomorphous. The compound crystallizes in the monoclinic system, space group P2(1)/n, with a=17.240(5), b=26.200(5), c=11.340(5) A, beta=101.320(5) degrees. DFT calculations were performed on the S=3/2 state to characterize the ground state potential energy surface as a function of the nuclear displacements. The molecules can thus be classified as Class III mixed-valence compounds with a computed delocalization parameter, B=3716, 3583, and 3261 cm(-1) for the Cl, Br, and I derivatives, respectively.

Structure and Magnetic Properties of a Mixed-Valence Heptanuclear Manganese Cluster.

Science.gov (United States)

Abbati, Gian Luca; Cornia, Andrea; Fabretti, Antonio C.; Caneschi, Andrea; Gatteschi, Dante

1998-07-27

Two novel polynuclear manganese(II,III) complexes have been synthesized by exploiting controlled methanolysis. A one-pot reaction of MnCl(2), NaOMe, dibenzoylmethane (Hdbm), and O(2) in anhydrous methanol, followed by recrystallization from MeOH/CHCl(3) mixtures, afforded the alkoxomanganese complexes [Mn(7)(OMe)(12)(dbm)(6)].CHCl(3).14MeOH (2) and [Mn(2)(OMe)(2)(dbm)(4)] (3). Complex 2 crystallizes in trigonal space group R&thremacr; with a = 14.439(2) Å, alpha = 86.34(1) degrees, and Z = 1. Complex 3 crystallizes in triclinic space group P&onemacr; with a = 9.612(1) Å, b = 10.740(1) Å, c = 13.168(1) Å, alpha = 80.39(1) degrees, beta = 87.66(1) degrees, gamma = 83.57(1) degrees, and Z = 1. The solid-state structure of 2 comprises a [Mn(6)(OMe)(12)(dbm)(6)] "crown" with crystallographically imposed 6-fold symmetry plus a central manganese ion. The layered Mn/O core mimics a fragment of the manganese oxide mineral lithiophorite. Conductivity measurements confirmed the nonionic character of 2 and suggested a mixed-valence Mn(II)(3)Mn(III)(4) formulation. The metrical parameters of the core were analyzed with the aid of bond-valence sum calculations. The central ion is essentially a valence-trapped Mn(II) ion, whereas the average Mn-O distances for the manganese ions of the "crown" are consistent with the presence of two Mn(II) and four Mn(III) ions. However, (1)H NMR spectra in solution strongly support valence localization and suggest that the observed solid-state structure may be a result of static disorder effects. Magnetic susceptibility vs T and magnetization vs field data at low temperature are consistent with an S = (17)/(2) ground state. Complex 3 is a symmetric alkoxo-bridged dimer. The two high-spin Mn(III) ions are antiferromagnetically coupled with J = 0.28(4) cm(-)(1), g = 1.983(2), and D = -2.5(4) cm(-)(1).

Not always a matter of context: direct effects of red on arousal but context-dependent moderations on valence

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Vanessa L. Buechner

2016-09-01

Full Text Available The arousal theory of color proposes that red is associated with arousal. Research on the color-in-context theory, in turn, states that the context in which red is perceived influences its valence-related meaning and behavioral responses to it. This study faces and integrates these theories by examining the influence of red on both arousal and valence perceptions of test-relevant and neutral stimuli, rendering a color 2 (red vs. blue × context 2 (test vs. neutral between-subjects design. Participants rated different pictures regarding their arousal and valence component, respectively. In line with the assumptions of both theories, red increased arousal perceptions of stimuli irrespective of their valence but a context × color interaction was found for valence perceptions: for participants viewing test-relevant pictures, red increased their perceptions of negativity compared to neutral pictures. The present study shows that both theories are actually compatible when differentiating the arousal and valence component.

Spectroscopy of 211Rn approaching the valence limit

International Nuclear Information System (INIS)

Davidson, P.M.; Dracoulis, G.D.; Byrne, A.P.; Kibedi, T.; Fabricus, B.; Baxter, A.M.; Stuchbery, A.E.; Poletti, A.R.; Schiffer, K.J.

1993-01-01

High-spin states in 211 Rn were populated using the reaction 198 Pt( 18 O, 5n) at 96 MeV. Their decay was studied using γ-ray and electron spectroscopy. The known level scheme is extended up to a spin of greater than 69/2 and many non-yrast states are added. Semi-empirical shell-model calculations and the properties of related states in 210 Rn and 212 Rn are used to assign configurations to some of the non-yrast states. The properties of the high-spin states observed are compared to the predictions of the multi-particle octupole-coupling model and the semi-empirical shell model. The maximum reasonable spin available from the valence particles and holes in 77/2 and states are observed to near this limit. (orig.)

Core and valence level photoemission and photoabsorption study of icosahedral Al-Pd-Mn quasicrystals

International Nuclear Information System (INIS)

Horn, K; Theis, W; Paggel, J J; Barman, S R; Rotenberg, E; Ebert, Ph; Urban, K

2006-01-01

The electronic structure of quasicrystalline Al-Pd-Mn is investigated by means of valence and core level photoelectron spectroscopy. Variations of the photoionization cross section in the constituents' valence electronic levels as a function of photon energy are used to identify contributions from the different atomic species, in particular near the Pd 4d Cooper minimum. Resonant photoemission at the Mn 2p absorption edge shows the contribution of the Mn 3d states to the density of states in a region near the Fermi level. The asymmetry of Pd 3d and Mn 2p core level photoemission lines, and its difference for emission from metallic and quasicrystalline phases, are utilized to infer the contributions of the different constituents to the density of states at the Fermi level

Systematic study on intermolecular valence-band dispersion in molecular crystalline films

International Nuclear Information System (INIS)

Yamane, Hiroyuki; Kosugi, Nobuhiro

2015-01-01

Highlights: • Intermolecular valence-band dispersion of crystalline films of phthalocyanines. • Intermolecular transfer integral versus lattice constant. • Site-specific intermolecular interaction and resultant valence-band dispersion. • Band narrowing effect induced by elevated temperature. - Abstract: Functionalities of organic semiconductors are governed not only by individual properties of constituent molecules but also by solid-state electronic states near the Fermi level such as frontier molecular orbitals, depending on weak intermolecular interactions in various conformations. The individual molecular property has been widely investigated in detail; on the other hand, the weak intermolecular interaction is difficult to investigate precisely due to the presence of the structural and thermal energy broadenings in organic solids. Here we show quite small but essential intermolecular valence band dispersions and their temperature dependence of sub-0.1-eV scale in crystalline films of metal phthalocyanines (H_2Pc, ZnPc, CoPc, MnPc, and F_1_6ZnPc) by using angle-resolved photoemission spectroscopy (ARPES) with synchrotron radiation. The observed bands show intermolecular and site dependent dispersion widths, phases, and periodicities, for different chemical substitution of terminal groups and central metals in the phthalocyanine molecule. The precise and systematic band-dispersion measurement would be a credible approach toward the comprehensive understanding of intermolecular interactions and resultant charge transport properties as well as their tuning by substituents in organic molecular systems.

Conditions for stability of different valence states of manganese impurity in α-Al2O3

International Nuclear Information System (INIS)

Kulagin, N.A.; Apanasenko, A.L.; Kazakov, N.A.

1983-01-01

The influence of crystal growth conditions on valence change of a Mn ion at γ-irradiation of corUndum has been studied. The results were obtained on an ESR-spectrome-- ter at 300 K. The crystals (except Mn ions) contained different impurities (Fe 3+ , Cr 3+ , Ti) and depending on the impurities on γ-irradiation, the transition of Mn 3+ both into Mn 3+ and Mn 4+ state or into one of them was observed. For several crystals (with Ti impOrity), the delta-like decrease of Csub(Mnsup(2+)) concentration is observed at 750+800 K and a full decrease of Csub(Mnsup(2+)) was obtained at 1100-1200 K.The results allow the conclusion of the possible mechanisms underlying the stabilization of Mn 2+ and Mn 4+ ions in corundum

Systematic thermodynamic properties of actinide metal-oxygen systems at high temperatures: Emphasis on lower valence states

International Nuclear Information System (INIS)

Ackermann, R.J.; Chandrasekharaiah, M.S.

1975-01-01

The thermodynamic data for the actinide metals and oxides (thorium to curium ) have been assessed, examined for consistency, and compared with the lanthanides. Correlations relating the enthalpies of formation of the solid oxides with the corresponding aquo ions make possible the estimation of the thermodynamic properties of AmO 2 (s) and Am 2 O 3 (s) which are in accordance with vaporization data. The known thermodynamic properties of the substoichiometric dioxides MOsub(2-x)(s) at high temperatures demonstrate the relative stabilities of valence states less than 4+ and lead to the examination of stability requirements for the sesquioxides M 2 O 3 (s) and the monoxides MO(s). Sequential trends in the gaseous metals, monoxides and dioxides are examined, compared, and contrasted with the lanthanides. (author)

Positive valence music restores executive control over sustained attention.

Science.gov (United States)

Baldwin, Carryl L; Lewis, Bridget A

2017-01-01

Music sometimes improves performance in sustained attention tasks. But the type of music employed in previous investigations has varied considerably, which can account for equivocal results. Progress has been hampered by lack of a systematic database of music varying in key characteristics like tempo and valence. The aims of this study were to establish a database of popular music varying along the dimensions of tempo and valence and to examine the impact of music varying along these dimensions on restoring attentional resources following performance of a sustained attention to response task (SART) vigil. Sixty-nine participants rated popular musical selections that varied in valence and tempo to establish a database of four musical types: fast tempo positive valence, fast tempo negative valence, slow tempo positive valence, and slow tempo negative valence. A second group of 89 participants performed two blocks of the SART task interspersed with either no break or a rest break consisting of 1 of the 4 types of music or silence. Presenting positive valence music (particularly of slow tempo) during an intermission between two successive blocks of the SART significantly decreased miss rates relative to negative valence music or silence. Results support an attentional restoration theory of the impact of music on sustained attention, rather than arousal theory and demonstrate a means of restoring sustained attention. Further, the results establish the validity of a music database that will facilitate further investigations of the impact of music on performance.

The possibility of the mixed valence state in the uranium intermetallic compounds: UCoGa5, U2Ru2Sn and U2RuGa8

International Nuclear Information System (INIS)

Troc, Robert

2007-01-01

The mixed valence (MV) phenomenon has been observed so far in a large number of various compounds but containing only lanthanides. These properties are usually associated with the mixing of the localised f-state and the band states. The usual valence state for magnetic uranium intermetallics is the trivalent state 5f 3 or hybridised 5f 2 6d 1 , both are nearly degenerate in energy and can compete for a stability of the compound. In some cases a gain in an energy minimum may be achieved by very fast fluctuating between these two states with a time of 10 -14 s, which does not allow to yield the ordered state even if the exchange interactions (favourite the U-U distances) would be able for that. The latter cases seem to concern the described here intermetallics: one ternary compound based on Co, UCoGa 5 , and the two uranium ternary compounds based on Ru, namely U 2 Ru 2 Sn and U 2 RuGa 8 which all crystallize in a tetragonal unit cell. All these compounds show a maximum in their temperature dependences of the magnetic susceptibility measured along and perpendicular to the c-axis. Such a behaviour, which is reminiscent of a number of Ce (Sm, Eu) and Yb compounds for which χ(T) has in the past been considered by Sales and Wohlleben (SW) by applying their ICF model or by Lawrance et al. following their scaling procedure. It turned out that these phenomenological models can also be applied to the considered here two Ru-based uranium ternaries from which some reliable energy parameters could be found. In order to further support the mixing valence scenario for the first such cases in uranium compounds presented here, the transport and thermodynamic properties are also discussed. However, some of the most important results confirming the MV state, e.g., in U 2 RuGa 8 , has recently been achieved from the inelastic neutron scattering performed in the Rutherford Appleton Laboratory on the ISIS facility. From these measurements a characteristic gap of 60 meV has been

NATO Advanced Study Institute on Mixed-Valence Compounds : Theory and Applications in Chemistry, Physics, Geology, and Biology

CERN Document Server

1980-01-01

It has been a decade since two seminal reviews demonstrated that mixed-valence compounds share many unique and fascinating features. The insight pro­ vided by those early works has promoted a great deal of both experimental and theoretical study. As a result of extensive efforts, our understanding of the bonding and properties of mixed-valence compounds has advanced substantially. There has been no compre­ hensive treatment of mixed-valence compounds since 1967, and the meeting convened at Oxford in September, 1979, provided a unique opportunity to examine the subject and its many ramifications. Mixed-valence compounds play an important role in many fields. Although the major impact of the subject has been in chemistry, its importance has become increasingly clear in solid state physics, geology, and biology. Extensive interest and effort in the field of molecular metals has demonstrated that mixed-valency is a prerequisite for high elec­ trical conductivity. The intense colors of many minerals have been s...

Valency and type conversion in CuInSe2 with H2 plasma exposure: A photoemission investigation

International Nuclear Information System (INIS)

Nelson, A.J.; Frigo, S.P.; Rosenberg, R.

1993-01-01

The effect of H 2 plasma exposure on CuInSe 2 was studied by synchrotron radiation soft-x-ray photoemission spectroscopy. The low-power H 2 plasma was generated with a commercial electron cyclotron resonance plasma source using pure H 2 with the plasma exposure being performed at 200 degree C. In situ photoemission measurements were acquired after each plasma exposure in order to observe changes in the valence-band electronic structure as well as changes in the In 4d and Se 3d core lines. The results were correlated in order to relate changes in surface chemistry to the electronic structure. These measurements indicate that the H 2 plasma exposure type converts the CuInSe 2 surface to an n-type surface as well as converting the In +3 valency state to an In +1 valency state

Exact valence bond entanglement entropy and probability distribution in the XXX spin chain and the potts model.

Science.gov (United States)

Jacobsen, J L; Saleur, H

2008-02-29

We determine exactly the probability distribution of the number N_(c) of valence bonds connecting a subsystem of length L>1 to the rest of the system in the ground state of the XXX antiferromagnetic spin chain. This provides, in particular, the asymptotic behavior of the valence-bond entanglement entropy S_(VB)=N_(c)ln2=4ln2/pi(2)lnL disproving a recent conjecture that this should be related with the von Neumann entropy, and thus equal to 1/3lnL. Our results generalize to the Q-state Potts model.

Effects of Electric Field on the Valence-Bond Property of an Electron in a Quantum-Dot Molecule

Institute of Scientific and Technical Information of China (English)

王立民; 罗莹; 马本堃

2002-01-01

The electronic structure of the quantum-dot molecules in an electric field is investigated by the finite element method with the effective mass approximation. The numerical calculation results show that the valence bond of the quantum-dot molecule alternates between covalent bonds and ionic bonds as the electric field increases. The valence-bond property can be reflected by the oscillator strength of the intraband transition. The bound state with the highest energy level in the quantum-dot molecule gradually changes into a quasibound state when the electric field increases.

Spectroscopy of 211Rn approaching the valence limit

International Nuclear Information System (INIS)

Davidson, P.M.; Dracoulis, G.D.; Kibedi, T.; Fabricius, B.; Baxter, A.M.; Stuchbery, A.E.; Poletti, A.R.; Schiffer, K.J.

1993-02-01

High spin states in 211 Rn were populated using the reaction 198 Pt( 18 O,5n) at 96 MeV. The decay was studied using γ-ray and electron spectroscopy. The known level scheme is extended up to a spin of greater than 69/2 and many non-yrast states are added. Semi-empirical shell model calculations and the properties of related states in 210 Rn and 212 Rn are used to assign configurations to some of the non-yrast states. The properties of the high spin states observed are compared to the predictions of the Multi-Particle Octupole Coupling model and the semi-empirical shell model. The maximum reasonable spin available from the valence particles and holes is 77/2 and states are observed to near this limit. 12 refs., 4 tabs., 8 figs

Architectural Representation of Valence in the Limbic System

Science.gov (United States)

Namburi, Praneeth; Al-Hasani, Ream; Calhoon, Gwendolyn G; Bruchas, Michael R; Tye, Kay M

2016-01-01

In order to thrive, animals must be able to recognize aversive and appetitive stimuli within the environment and subsequently initiate appropriate behavioral responses. This assignment of positive or negative valence to a stimulus is a key feature of emotional processing, the neural substrates of which have been a topic of study for several decades. Until recently, the result of this work has been the identification of specific brain regions, such as the basolateral amygdala (BLA) and nucleus accumbens (NAc), as important to valence encoding. The advent of modern tools in neuroscience has allowed further dissection of these regions to identify specific populations of neurons signaling the valence of environmental stimuli. In this review, we focus upon recent work examining the mechanisms of valence encoding, and provide a model for the systematic investigation of valence within anatomically-, genetically-, and functionally defined populations of neurons. PMID:26647973

Production and characterization of yeast cytochrome c antibodies; immunological studies of mutants with altered cytochrome c synthesis

International Nuclear Information System (INIS)

Matner, R.R.

1980-01-01

Mutations at the structural gene, CYC1, for iso-1-cytochrome c and at the structural gene, CYC7, for iso-2-cytochrome c can reduce the levels of the respective proteins by varying degrees in Saccharomyces cerevisiae. Mutations at two other loci, cyc2 and cyc3, that are unlinked to either of the structural genes, specifically reduced the levels of both iso-cytochromes c. The cyc2 mutations can cause as low as 10 to 20% of the normal level and cyc3 mutations can cause complete deficiencies. We have explored the possiblity that the CYC2 and CYC3 loci code for maturation functions in the biosynthesis of cytochrome c. The approach used to characterize the nature of the cyc2 and cyc3 induced deficiencies of cytochrome c involved four steps. The results were used to propose possible roles for the CYC2 and CYC3 encoded functions. The CYC3 encoded function is hypothesized to be enzymatic heme attachment. CYC2 may code for a protein that binds and transports apo-cytochrome c through the outer mitochondrial membrane and/or enhances the activity of the heme attachment enzyme

On triangle meshes with valence dominant vertices

KAUST Repository

Morvan, Jean-Marie

2018-02-16

We study triangulations $\\\\cal T$ defined on a closed disc $X$ satisfying the following condition: In the interior of $X$, the valence of all vertices of $\\\\cal T$ except one of them (the irregular vertex) is $6$. By using a flat singular Riemannian metric adapted to $\\\\cal T$, we prove a uniqueness theorem when the valence of the irregular vertex is not a multiple of $6$. Moreover, for a given integer $k >1$, we exhibit non isomorphic triangulations on $X$ with the same boundary, and with a unique irregular vertex whose valence is $6k$.

On triangle meshes with valence dominant vertices

KAUST Repository

Morvan, Jean-Marie

2018-01-01

We study triangulations $\\cal T$ defined on a closed disc $X$ satisfying the following condition: In the interior of $X$, the valence of all vertices of $\\cal T$ except one of them (the irregular vertex) is $6$. By using a flat singular Riemannian metric adapted to $\\cal T$, we prove a uniqueness theorem when the valence of the irregular vertex is not a multiple of $6$. Moreover, for a given integer $k >1$, we exhibit non isomorphic triangulations on $X$ with the same boundary, and with a unique irregular vertex whose valence is $6k$.

Magnetic-field control of quantum critical points of valence transition.

Science.gov (United States)

Watanabe, Shinji; Tsuruta, Atsushi; Miyake, Kazumasa; Flouquet, Jacques

2008-06-13

We study the mechanism of how critical end points of first-order valence transitions are controlled by a magnetic field. We show that the critical temperature is suppressed to be a quantum critical point (QCP) by a magnetic field, and unexpectedly, the QCP exhibits nonmonotonic field dependence in the ground-state phase diagram, giving rise to the emergence of metamagnetism even in the intermediate valence-crossover regime. The driving force of the field-induced QCP is clarified to be cooperative phenomena of the Zeeman and Kondo effects, which create a distinct energy scale from the Kondo temperature. This mechanism explains the peculiar magnetic response in CeIrIn(5) and the metamagnetic transition in YbXCu(4) for X=In as well as the sharp contrast between X=Ag and Cd.

Few-valence-particle excitations around doubly magic 132Sn

International Nuclear Information System (INIS)

Daly, P.J.; Zhang, C.T.; Bhattacharyya, P.

1996-01-01

Prompt γ-ray cascades in neutron-rich nuclei around doubly-magic 132 Sn have been studied using a 248 Cm fission source. Yrast states located in the N = 82 isotones 134 Te and 135 I are interpreted as valence proton and neutron particle-hole core excitations with the help of shell model calculations employing empirical nucleon-nucleon interactions from both 132 Sn and 208 Pb regions

Social learning modulates the lateralization of emotional valence.

Science.gov (United States)

Shamay-Tsoory, Simone G; Lavidor, Michal; Aharon-Peretz, Judith

2008-08-01

Although neuropsychological studies of lateralization of emotion have emphasized valence (positive vs. negative) or type (basic vs. complex) dimensions, the interaction between the two dimensions has yet to be elucidated. The purpose of the current study was to test the hypothesis that recognition of basic emotions is processed preferentially by the right prefrontal cortex (PFC), whereas recognition of complex social emotions is processed preferentially by the left PFC. Experiment 1 assessed the ability of healthy controls and patients with right and left PFC lesions to recognize basic and complex emotions. Experiment 2 modeled the patient's data of Experiment 1 on healthy participants under lateralized displays of the emotional stimuli. Both experiments support the Type as well as the Valence Hypotheses. However, our findings indicate that the Valence Hypothesis holds for basic but less so for complex emotions. It is suggested that, since social learning overrules the basic preference of valence in the hemispheres, the processing of complex emotions in the hemispheres is less affected by valence.

Valence of Facial Cues Influences Sheep Learning in a Visual Discrimination Task

Directory of Open Access Journals (Sweden)

Lucille G. A. Bellegarde

2017-11-01

Full Text Available Sheep are one of the most studied farm species in terms of their ability to process information from faces, but little is known about their face-based emotion recognition abilities. We investigated (a whether sheep could use images of sheep faces taken in situation of varying valence as cues in a simultaneous discrimination task and (b whether the valence of the situation affects their learning performance. To accomplish this, we photographed faces of sheep in three situations inducing emotional states of neutral (ruminating in the home pen or negative valence (social isolation or aggressive interaction. Sheep (n = 35 first had to learn a discrimination task with colored cards. Animals that reached the learning criterion (n = 16 were then presented with pairs of images of the face of a single individual taken in the neutral situation and in one of the negative situations. Finally, sheep had to generalize what they had learned to new pairs of images of faces taken in the same situation, but of a different conspecific. All sheep that learned the discrimination task with colored cards reached the learning criterion with images of faces. Sheep that had to associate a negative image with a food reward learned faster than sheep that had to associate a neutral image with a reward. With the exception of sheep from the aggression-rewarded group, sheep generalized this discrimination to images of faces of different individuals. Our results suggest that sheep can perceive the emotional valence displayed on faces of conspecifics and that this valence affects learning processes.

The localized effect of the Bi level on the valence band in the dilute bismuth GaBixAs1-x alloy

Science.gov (United States)

Zhao, Chuan-Zhen; Zhu, Min-Min; Wang, Jun; Wang, Sha-Sha; Lu, Ke-Qing

2018-05-01

The research on the temperature dependence of the band gap energy of the dilute bismuth GaBixAs1-x alloy has been done. It is found that its temperature insensitiveness is due to the enhanced localized character of the valence band state and the small decrease of the temperature coefficient for the conduction band minimum (CBM). The enhanced localized character of the valence band state is the main factor. In order to describe the localized effect of the Bi levels on the valence band, the localized energy is introduced into the Varshni's equation. It is found that the effect of the localized Bi level on the valence band becomes strong with increasing Bi content. In addition, it is found that the pressure dependence of the band gap energy of GaBixAs1-x does not seem to be influenced by the localized Bi levels. It is due to two factors. One is that the pressure dependence of the band gap energy is mainly determined by the D CBM of GaBixAs1-x. The D CBM of GaBixAs1-x is not influenced by the localized Bi levels. The other is that the small variation of the pressure coefficient for the D valence band maximum (VBM) state of GaBixAs1-x can be cancelled by the variation of the pressure coefficient for the D CBM state of GaBixAs1-x.

Determination of valence band parameters in ZnTe

Energy Technology Data Exchange (ETDEWEB)

Froehlich, D.; Noethe, A.; Reimann, K. (Duesseldorf Univ. (Germany, F.R.). Physikalisches Inst. - Lehrstuhl 2)

1984-10-01

The fine structure of the 2P exciton in ZnTe is studied by two-photon-absorption. The energy splitting into four states, caused by the envelope-hole coupling, allows the determination of the Luttinger parameters ..gamma../sub 2/ and ..gamma../sub 3/, which describe the complex valence band. ..gamma../sub 2/ = 0.8 and ..gamma../sub 3/ = 1.7 are obtained. These values are compared to results of other experiments mainly on 1S excitons.

Valence nucleons in self-consistent fields

International Nuclear Information System (INIS)

Di Toro, M.; Lomnitz-Adler, J.

1978-01-01

An iterative approach to determine directly the best Hartree-Fock one-body density rho is extended by expressing rho in terms of a core and a valence part and allowing for general crossings of occupied and unoccupied levels in the valence part. Results are shown for 152 Sm and a microscopic analysis of the core structure of deformed light nuclei is carried out. (author)

Calculation of fluctuations and photoemission properties in a tetrahedral-cluster model for an intermediate-valence system

International Nuclear Information System (INIS)

Reich, A.; Falicov, L.M.

1986-01-01

An exact solution of a four-site tetrahedral-crystal model, the smallest face-centered-cubic crystal, is presented in the case of an intermediate-valence system. The model consists of the following: (a) one extended orbital and one localized orbital per atom, (b) an interatomic transfer term between extended orbitals, (c) an interatomic hybridization between the localized and extended orbitals, (d) strong intra-atomic Coulomb repulsion between opposite-spin localized states, and (e) intermediate-strength intra-atomic Coulomb repulsion between the localized and extended states. These competing effects are examined as they manifest themselves in the intermediate-valence, photoemission, inverse-photoemission, and thermodynamic properties

NiMn layered double hydroxide nanosheets/NiCo2O4 nanowires with surface rich high valence state metal oxide as an efficient electrocatalyst for oxygen evolution reaction

Science.gov (United States)

Yang, Liting; Chen, Lin; Yang, Dawen; Yu, Xu; Xue, Huaiguo; Feng, Ligang

2018-07-01

High valence transition metal oxide is significant for anode catalyst of proton membrane water electrolysis technique. Herein, we demonstrate NiMn layered double hydroxide nanosheets/NiCo2O4 nanowires hierarchical nanocomposite catalyst with surface rich high valence metal oxide as an efficient catalyst for oxygen evolution reaction. A low overpotential of 310 mV is needed to drive a 10 mA cm-2 with a Tafel slope of 99 mV dec-1, and a remarkable stability during 8 h is demonstrated in a chronoamperometry test. Theoretical calculation displays the change in the rate-determining step on the nanocomposite electrode in comparison to NiCo2O4 nanowires alone. It is found high valence Ni and Mn oxide in the catalyst system can efficiently facilitate the charge transport across the electrode/electrolyte interface. The enhanced electrical conductivity, more accessible active sites and synergistic effects between NiMn layered double hydroxide nanosheets and NiCo2O4 nanowires can account for the excellent oxygen evolution reaction. The catalytic performance is comparable to most of the best non-noble catalysts and IrO2 noble catalyst, indicating the promising applications in water-splitting technology. It is an important step in the development of hierarchical nanocomposites by surface valence state tuning as an alternative to noble metals for oxygen evolution reaction.

Fluorescence properties of valence-controlled Eu2+ and Mn2+ ions in aluminosilicate glasses

International Nuclear Information System (INIS)

Van Tuyen, Ho; Nonaka, Takamasa; Yamanaka, Ken-ichi; Chau, Pham Minh; Quy Hai, Nguyen Thi; Quang, Vu Xuan; Nogami, Masayuki

2017-01-01

Controlling of valence states of metal ions doped in glasses has attracted considerable interest due to the possibility of looking toward optical applications. In this study, new Na 2 O-Al 2 O 3 -SiO 2 glasses were developed to dope Eu 2+ and Mn 2+ with well controlled valence states by heating in H 2 gas atmosphere, and the changes in the valence state of doped-ions and their fluorescence properties were investigated using visible and infrared optical absorption spectroscopies, X-ray absorption fine structure spectroscopy, and fluorescence spectroscopy. Among Eu 3+ , Mn 3+ and Mn 2+ ions incorporated in the as-prepared glasses, the Eu 3+ and Mn 3+ ions were reduced to Eu 2+ and Mn 2+ ions, respectively, by heating in H 2 gas and OH bonds were concurrently formed. The fluorescence spectra of glasses heated in H 2 exhibited broad emission bands at 450 and 630 nm wavelength, assigned to the Eu 2+ and Mn 2+ , respectively, ions, in which the fluorescence intensity at 450 nm was observed to decrease with increasing Mn 2+ ion content. The increased fluorescence intensities were analyzed as the energy transfer from Eu 2+ to Mn 2+ ions and the energy transfer efficiency was estimated with a concentration of Eu 2+ and Mn 2+ ions.

Neural mechanisms underlying valence inferences to sound: The role of the right angular gyrus.

Science.gov (United States)

Bravo, Fernando; Cross, Ian; Hawkins, Sarah; Gonzalez, Nadia; Docampo, Jorge; Bruno, Claudio; Stamatakis, Emmanuel Andreas

2017-07-28

We frequently infer others' intentions based on non-verbal auditory cues. Although the brain underpinnings of social cognition have been extensively studied, no empirical work has yet examined the impact of musical structure manipulation on the neural processing of emotional valence during mental state inferences. We used a novel sound-based theory-of-mind paradigm in which participants categorized stimuli of different sensory dissonance level in terms of positive/negative valence. Whilst consistent with previous studies which propose facilitated encoding of consonances, our results demonstrated that distinct levels of consonance/dissonance elicited differential influences on the right angular gyrus, an area implicated in mental state attribution and attention reorienting processes. Functional and effective connectivity analyses further showed that consonances modulated a specific inhibitory interaction from associative memory to mental state attribution substrates. Following evidence suggesting that individuals with autism may process social affective cues differently, we assessed the relationship between participants' task performance and self-reported autistic traits in clinically typical adults. Higher scores on the social cognition scales of the AQ were associated with deficits in recognising positive valence in consonant sound cues. These findings are discussed with respect to Bayesian perspectives on autistic perception, which highlight a functional failure to optimize precision in relation to prior beliefs. Copyright © 2017 Elsevier Ltd. All rights reserved.

Nature of the magnetic ground state in the mixed valence compound CeRuSn: a single-crystal study

International Nuclear Information System (INIS)

Fikáček, J; Prokleška, J; Prchal, J; Custers, J; Sechovský, V

2013-01-01

We report on detailed low-temperature measurements of the magnetization, the specific heat and the electrical resistivity on high-quality CeRuSn single crystals. The compound orders antiferromagnetically at T N = 2.8 K with the Ce 3+ ions locked within the a–c plane of the monoclinic structure. Magnetization shows that below T N CeRuSn undergoes a metamagnetic transition when applying a magnetic field of 1.5 and 0.8 T along the a- and c-axis, respectively. This transition manifests in a tremendous negative jump of ∼25% in the magnetoresistance. The value of the saturated magnetization along the easy magnetization direction (c-axis) and the magnetic entropy above T N derived from specific heat data correspond to the scenario of only one third of the Ce ions in the compound being trivalent and carrying a stable Ce 3+ magnetic moment, whereas the other two thirds of the Ce ions are in a nonmagnetic tetravalent and/or mixed valence state. This is consistent with the low-temperature CeRuSn crystal structure i.e., a superstructure consisting of three unit cells of the CeCoAl type piled up along the c-axis, and in which the Ce 3+ ions are characterized by large distances from the Ru ligands while the Ce–Ru distances of the other Ce ions are much shorter causing a strong 4f-ligand hybridization and hence leading to tetravalent and/or mixed valence Ce ions. (paper)

Isotopic exchange in mixed valence compounds in the solid state

International Nuclear Information System (INIS)

Fernandez Valverde, S.M.

1986-01-01

This work aims at the determination of isotopic exchange kinetics and mechanism in two mixed valence compounds: Cs 10 (Sbsup(V)Cl 6 ) (Sbsup(III)Cl 6 ) 3 and Tl 3 sup(I)(Tlsup(III)Cl 6 ). The synthesis of the first compound is very difficult because in most of the cases mixtures of chloroantimoniates are obtained. Exchange in Tl 4 Cl 6 labelled on Tlsup(III) is studied in detail by radiochemical analysis and physical techniques: ionic conductivity and positon annihilation. Cation vacancies are easily created in the lattice with formation enthalpy of 0.35 eV and migration enthalpy of 0.52 eV. Isochronic and isothermal exchange curves are described by a kinetic based on species diffusion. Models are given. Exchange is increased by grinding probably because extrinseque defects are introduced [fr

Calcium transport in vesicles energized by cytochrome oxidase

Energy Technology Data Exchange (ETDEWEB)

Rosier, Randy N. [Univ. of Rochester, NY (United States)

1979-01-01

Experiments on the reconstitution of cytochrome oxidase into phospholipid vesicles were carried out using techniques of selectivity energizing the suspensions with ascorbate and cytochrome c or ascorbate, PMS, and internally trapped cytochrome c. It was found that the K⁺ selective ionophore valinomycin stimulated the rate of respiration of cytochrome oxidase vesicles regardless of the direction of the K⁺ flux across the vesicle membranes. The stimulation occurred in the presence of protonophoric uncouplers and in the complete absence of potassium or in detergent-lysed suspensions. Gramicidin had similar effects and it was determined that the ionophores acted by specific interaction with cytochrome oxidase rather than by the previously assumed collapse of membrane potentials. When hydrophobic proteins and appropriate coupling factors were incorporated into the cytochrome oxidase, vesicles phosphorylation of ADP could be coupled to the oxidation reaction of cytochrome oxidase. Relatively low P:O, representing poor coupling of the system, were problematical and precluded measurements of protonmotive force. However the system was used to study ion translocation.

Probing Transient Valence Orbital Changes with Picosecond Valence-to-Core X-ray Emission Spectroscopy

DEFF Research Database (Denmark)

March, Anne Marie; Assefa, Tadesse A.; Boemer, Christina

2017-01-01

We probe the dynamics of valence electrons in photoexcited [Fe(terpy)2]2+ in solution to gain deeper insight into the Fe ligand bond changes. We use hard X-ray emission spectroscopy (XES), which combines element specificity and high penetration with sensitivity to orbital structure, making...... valence orbitals to the nascent core-hole. Vtc-XES offers particular insight into the molecular orbitals directly involved in the light-driven dynamics; a change in the metal ligand orbital overlap results in an intensity reduction and a blue energy shift in agreement with our theoretical calculations...... and more subtle features at the highest energies reflect changes in the frontier orbital populations....

Cytochrome c interaction with hematite ({alpha}-Fe{sub 2}O{sub 3}) surfaces

Energy Technology Data Exchange (ETDEWEB)

Eggleston, Carrick M. [Department of Geology and Geophysics, University of Wyoming, Laramie, WY 82071 (United States)]. E-mail: carrick@uwyo.edu; Khare, Nidhi [Department of Geology and Geophysics, University of Wyoming, Laramie, WY 82071 (United States); Lovelace, David M. [Department of Geology and Geophysics, University of Wyoming, Laramie, WY 82071 (United States)

2006-02-15

The interaction of metalloproteins such as cytochromes with oxides is of interest for a number of reasons, including molecular catalysis of environmentally important mineral-solution electron transfer reactions (e.g., dehalogenations) and photovoltaic applications. Iron reduction by bacteria, thought to be cytochrome mediated, is of interest for geochemical and environmental remediation reasons. As a baseline for understanding cytochrome interaction with ferric oxide surfaces, we report on the interaction of mitochondrial cytochrome c (Mcc), a well-studied protein, with hematite ({alpha}-Fe{sub 2}O{sub 3}) surfaces. Mcc sorbs strongly to hematite from aqueous solution in a narrow pH range corresponding to opposite charge on Mcc and hematite (between pH 8.5 and 10, Mcc is positively charged and hematite surfaces are negatively charged). Cyclic voltammetry of Mcc using hematite electrodes gives redox potentials characteristic of Mcc in a native conformational state, with no evidence for unfolding on the hematite surface. Atomic force microscopy imaging is consistent with a loosely attached adsorbate that is easily deformed by the AFM tip. In phosphate-containing solution, Mcc adhers to the surface more strongly. These results establish hematite as a viable material for electrochemical and spectroscopic characterization of cytochrome-mineral interaction.

Features of the core-valence luminescence and electron energy band structure of A1-xCsxCaCl3 (A = K,Rb) crystals

International Nuclear Information System (INIS)

Chornodolskyy, Ya; Stryganyuk, G; Syrotyuk, S; Voloshinovskii, A; Rodnyi, P

2007-01-01

From luminescence spectroscopy of CsCaCl 3 , Rb 1-x Cs x CaCl 3 and K 1-x Cs x CaCl 3 crystals, we have found evidence for intrinsic and impurity core-valence luminescence due to the radiative recombination of valence electrons with the holes of intrinsic or impurity 5p Cs + core states. The structural similarity of core-valence luminescence spectra has been revealed for the A 1-x Cs x CaCl 3 (A = K,Rb) crystals investigated. The electron energy structure of the CsCaCl 3 crystal has been calculated using the pseudopotential approach taking into account the gradient corrections for the exchange-correlation energy. The calculated density of the electronic states of CsCaCl 3 has been compared with corresponding parameters obtained from the analysis of core-valence luminescence spectra

Surface-site-selective study of valence electronic states of a clean Si(111)-7x7 surface using Si L23VV Auger electron and Si 2p photoelectron coincidence measurements

International Nuclear Information System (INIS)

Kakiuchi, Takuhiro; Tahara, Masashi; Nagaoka, Shin-ichi; Hashimoto, Shogo; Fujita, Narihiko; Tanaka, Masatoshi; Mase, Kazuhiko

2011-01-01

Valence electronic states of a clean Si(111)-7x7 surface are investigated in a surface-site-selective way using high-resolution coincidence measurements of Si pVV Auger electrons and Si 2p photoelectrons. The Si L 23 VV Auger electron spectra measured in coincidence with energy-selected Si 2p photoelectrons show that the valence band at the highest density of states in the vicinity of the rest atoms is shifted by ∼0.95 eV toward the Fermi level (E F ) relative to that in the vicinity of the pedestal atoms (atoms directly bonded to the adatoms). The valence-band maximum in the vicinity of the rest atoms, on the other hand, is shown to be shifted by ∼0.53 eV toward E F relative to that in the vicinity of the pedestal atoms. The Si 2p photoelectron spectra of Si(111)-7x7 measured in coincidence with energy-selected Si L 23 VV Auger electrons identify the topmost surface components, and suggest that the dimers and the rest atoms are negatively charged while the pedestal atoms are positively charged. Furthermore, the Si 2p-Si L 23 VV photoelectron Auger coincidence spectroscopy directly verifies that the adatom Si 2p component (usually denoted by C 3 ) is correlated with the surface state just below E F (usually denoted by S 1 ), as has been observed in previous angle-resolved photoelectron spectroscopy studies.

NMR comparison of prokaryotic and eukaryotic cytochromes c

International Nuclear Information System (INIS)

Chau, Meihing; Cai, Meng Li; Timkovich, R.

1990-01-01

1 H NMR spectroscopy has been used to examine ferrocytochrome c-551 from Pseudomonas aeruginosa (ATCC 19429) over the pH range 3.5-10.6 and the temperature range 4-60 degree C. Resonance assignments are proposed for main-chain and side-chain protons. Comparison of results for cytochrome c-551 to recently assigned spectra for horse cytochrome c and mutants of yeast iso-1 cytochrome reveals some unique resonances with unusual chemical shifts in all cytochromes that may serve as markers for the heme region. Results for cytochrome c-551 indicate that in the smaller prokaryotic cytochrome, all benzoid side chains are rapidly flipping on the NMR time scale. In contrast, in eukaryotic cytochromes there are some rings flipping slowly on the NMR time scale. The ferrocytochrome c-551 undergoes a transition linked to pH with a pK around 7. The pH behavior of assigned resonances provides evidence that the site of protonation is the inner or buried 17-propionic acid heme substituent (IUPAC-IUB porphyrin nomenclature). Conformational heterogeneity has been observed for segments near the inner heme propionate substituent

Similar Transition States Mediate the Q-cycle and Superoxide Production by the Cytochrome bc1 Complex

International Nuclear Information System (INIS)

Forquer, Isaac P.; Covian, Raul; Bowman, Michael K.; Trumpower, Bernard; Kramer, David M.

2006-01-01

The cytochrome bc complexes found in mitochondria, chloroplasts and many bacteria catalyze a critical reaction in their respective electron transport chains. The quinol oxidase (Qo) site in this complex oxidizes a hydroquinone (quinol), reducing two one-electron carriers, a low-potential cytochrome b heme and a ''Rieske'' iron-sulfur cluster. The overall electron transfer reactions are coupled to transmembrane translocation of protons via a ''Q-cycle'' mechanism, which generates proton motive force for ATP synthesis. Since semiquinone intermediates of quinol oxidation are generally highly reactive, one of the key questions in this field is: how does the Qo site oxidize quinol without the production of deleterious side reactions including superoxide production? We attempt to test three possible general models to account for this behavior: (1) The Qo site semiquinone (or quinol:imidazolate complex) is unstable and thus occurs at a very low steady-state concentration, limiting O2 reduction; (2) the Qo site semiquinone is highly stabilized making it unreactive towards oxygen; and (3) the Qo site catalyzes a quantum mechanically-coupled two-electron/two proton transfer without a semiquinone intermediate. Enthalpies of activation were found to be almost identical between the uninhibited Q-cycle and superoxide production in the presence of Antimycin A in wild type. This behavior was also preserved in a series of mutants with altered driving forces for quinol oxidation. Overall, the data supports models where the rate-limiting step for both Q-cycle and superoxide production are essentially identical, consistent with model 1 but requiring modifications to models 2 and 3

Valence-Dependent Belief Updating: Computational Validation

Directory of Open Access Journals (Sweden)

Bojana Kuzmanovic

2017-06-01

Full Text Available People tend to update beliefs about their future outcomes in a valence-dependent way: they are likely to incorporate good news and to neglect bad news. However, belief formation is a complex process which depends not only on motivational factors such as the desire for favorable conclusions, but also on multiple cognitive variables such as prior beliefs, knowledge about personal vulnerabilities and resources, and the size of the probabilities and estimation errors. Thus, we applied computational modeling in order to test for valence-induced biases in updating while formally controlling for relevant cognitive factors. We compared biased and unbiased Bayesian models of belief updating, and specified alternative models based on reinforcement learning. The experiment consisted of 80 trials with 80 different adverse future life events. In each trial, participants estimated the base rate of one of these events and estimated their own risk of experiencing the event before and after being confronted with the actual base rate. Belief updates corresponded to the difference between the two self-risk estimates. Valence-dependent updating was assessed by comparing trials with good news (better-than-expected base rates with trials with bad news (worse-than-expected base rates. After receiving bad relative to good news, participants' updates were smaller and deviated more strongly from rational Bayesian predictions, indicating a valence-induced bias. Model comparison revealed that the biased (i.e., optimistic Bayesian model of belief updating better accounted for data than the unbiased (i.e., rational Bayesian model, confirming that the valence of the new information influenced the amount of updating. Moreover, alternative computational modeling based on reinforcement learning demonstrated higher learning rates for good than for bad news, as well as a moderating role of personal knowledge. Finally, in this specific experimental context, the approach based on

Emotion and language: Valence and arousal affect word recognition

Science.gov (United States)

Brysbaert, Marc; Warriner, Amy Beth

2014-01-01

Emotion influences most aspects of cognition and behavior, but emotional factors are conspicuously absent from current models of word recognition. The influence of emotion on word recognition has mostly been reported in prior studies on the automatic vigilance for negative stimuli, but the precise nature of this relationship is unclear. Various models of automatic vigilance have claimed that the effect of valence on response times is categorical, an inverted-U, or interactive with arousal. The present study used a sample of 12,658 words, and included many lexical and semantic control factors, to determine the precise nature of the effects of arousal and valence on word recognition. Converging empirical patterns observed in word-level and trial-level data from lexical decision and naming indicate that valence and arousal exert independent monotonic effects: Negative words are recognized more slowly than positive words, and arousing words are recognized more slowly than calming words. Valence explained about 2% of the variance in word recognition latencies, whereas the effect of arousal was smaller. Valence and arousal do not interact, but both interact with word frequency, such that valence and arousal exert larger effects among low-frequency words than among high-frequency words. These results necessitate a new model of affective word processing whereby the degree of negativity monotonically and independently predicts the speed of responding. This research also demonstrates that incorporating emotional factors, especially valence, improves the performance of models of word recognition. PMID:24490848

A Comparison of the Valence Band Structure of Bulk and Epitaxial GeTe-based Diluted Magnetic Semiconductors

International Nuclear Information System (INIS)

Pietrzyk, M.A.; Kowalski, B.J.; Orlowski, B.A.; Knoff, W.; Story, T.; Dobrowolski, W.; Slynko, V.E.; Slynko, E.I.; Johnson, R.L.

2010-01-01

In this work we present a comparison of the experimental results, which have been obtained by the resonant photoelectron spectroscopy for a set of selected diluted magnetic semiconductors based on GeTe, doped with manganese. The photoemission spectra are acquired for the photon energy range of 40-60 eV, corresponding to the Mn 3p → 3d resonances. The spectral features related to Mn 3d states are revealed in the emission from the valence band. The Mn 3d states contribution manifests itself in the whole valence band with a maximum at the binding energy of 3.8 eV. (authors)

Valenced cues and contexts have different effects on event-based prospective memory.

Science.gov (United States)

Graf, Peter; Yu, Martin

2015-01-01

This study examined the separate influence and joint influences on event-based prospective memory task performance due to the valence of cues and the valence of contexts. We manipulated the valence of cues and contexts with pictures from the International Affective Picture System. The participants, undergraduate students, showed higher performance when neutral compared to valenced pictures were used for cueing prospective memory. In addition, neutral pictures were more effective as cues when they occurred in a valenced context than in the context of neutral pictures, but the effectiveness of valenced cues did not vary across contexts that differed in valence. The finding of an interaction between cue and context valence indicates that their respective influence on event-based prospective memory task performance cannot be understood in isolation from each other. Our findings are not consistent with by the prevailing view which holds that the scope of attention is broadened and narrowed, respectively, by positively and negatively valenced stimuli. Instead, our findings are more supportive of the recent proposal that the scope of attention is determined by the motivational intensity associated with valenced stimuli. Consistent with this proposal, we speculate that the motivational intensity associated with different retrieval cues determines the scope of attention, that contexts with different valence values determine participants' task engagement, and that prospective memory task performance is determined jointly by attention scope and task engagement.

Valenced cues and contexts have different effects on event-based prospective memory.

Directory of Open Access Journals (Sweden)

Peter Graf

Full Text Available This study examined the separate influence and joint influences on event-based prospective memory task performance due to the valence of cues and the valence of contexts. We manipulated the valence of cues and contexts with pictures from the International Affective Picture System. The participants, undergraduate students, showed higher performance when neutral compared to valenced pictures were used for cueing prospective memory. In addition, neutral pictures were more effective as cues when they occurred in a valenced context than in the context of neutral pictures, but the effectiveness of valenced cues did not vary across contexts that differed in valence. The finding of an interaction between cue and context valence indicates that their respective influence on event-based prospective memory task performance cannot be understood in isolation from each other. Our findings are not consistent with by the prevailing view which holds that the scope of attention is broadened and narrowed, respectively, by positively and negatively valenced stimuli. Instead, our findings are more supportive of the recent proposal that the scope of attention is determined by the motivational intensity associated with valenced stimuli. Consistent with this proposal, we speculate that the motivational intensity associated with different retrieval cues determines the scope of attention, that contexts with different valence values determine participants' task engagement, and that prospective memory task performance is determined jointly by attention scope and task engagement.

Negative pressure driven valence instability of Eu in cubic Eu0.4La0.6Pd3

International Nuclear Information System (INIS)

Pandey, Abhishek; Mazumdar, Chandan; Ranganathan, R

2009-01-01

We report the change in the valency of Eu-ions in the binary intermetallic cubic compound EuPd 3 induced by La doping at rare-earth sites. Doping of La generates negative chemical pressure in the lattice, resulting in a significant increase of the lattice parameter without altering the simple-cubic structure of the compound. Results of dc-magnetic measurements suggest that this increase in the lattice parameter is associated with the valence transition of Eu-ions from Eu 3+ to a mixed-valent state. As Eu 2+ -ions possess a large magnetic moment, this valence transition significantly modifies the magnetic behavior of the compound. In contrast to introducing boron at the vacant body center site of the unit cell to change the valency of Eu-ions, as in the case of EuPd 3 B, our results suggest it can also be altered by doping a rare-earth ion of larger size at the lattice site of Eu in EuPd 3 .

Neutron scattering studies of mixed-valence semiconductors

Energy Technology Data Exchange (ETDEWEB)

Mignot, J M [Laboratoire Leon Brillouin (LLB) - Centre d` Etudes de Saclay, 91 - Gif-sur-Yvette (France); Alekseev, P A [Kurchatov Institute, Moscow (Russian Federation)

1994-12-31

Neutron scattering experiments on the mixed-valence (MV) compounds SmB{sub 6} are reported. The inelastic magnetic response of SmB{sub 6} at T = 2 K, measured on a double-isotope single crystal,displays a strongly damped peak at 35 meV corresponding to the inter multiplet transition of Sm{sup 2+}. At lower energies ( h.{omega} {approx_equal} 14 meV), a narrow magnetic excitation is observed, with remarkable scattering-vector and temperature dependences of its intensity. This novel feature is discussed in terms of recent theoretical works describing the formation of an anisotropic local bound state in semiconducting MV materials. If the average samarium valence is decreased by substituting La for Sm, a peak is found to appear at high energies. The elastic magnetic form factor of SmB{sub 6} was determined using polarised neutrons and no significant difference is observed in its Q-dependence with respect to that of pure divalent samarium. This surprising behaviour is constant with previous measurements on the gold (high-pressure) phase of SmS. The above results are compared to those already reported for other MV materials. In particular existing information for TmSe is supplemented by recent inelastic scattering measurements carried out on a large stoichiometric single crystal. (author). 44 refs., 7 figs.

Decoding emotional valence from electroencephalographic rhythmic activity.

Science.gov (United States)

Celikkanat, Hande; Moriya, Hiroki; Ogawa, Takeshi; Kauppi, Jukka-Pekka; Kawanabe, Motoaki; Hyvarinen, Aapo

2017-07-01

We attempt to decode emotional valence from electroencephalographic rhythmic activity in a naturalistic setting. We employ a data-driven method developed in a previous study, Spectral Linear Discriminant Analysis, to discover the relationships between the classification task and independent neuronal sources, optimally utilizing multiple frequency bands. A detailed investigation of the classifier provides insight into the neuronal sources related with emotional valence, and the individual differences of the subjects in processing emotions. Our findings show: (1) sources whose locations are similar across subjects are consistently involved in emotional responses, with the involvement of parietal sources being especially significant, and (2) even though the locations of the involved neuronal sources are consistent, subjects can display highly varying degrees of valence-related EEG activity in the sources.

Virtual Distance and Soundstage, and their Impacts on Experienced Emotional Valence

DEFF Research Database (Denmark)

Christensen, Justin

2015-01-01

stimuli should cause stronger valenced responses in the nearfield than at a distance. Thus, music experienced as being negatively valenced at a distance should be more negatively valenced in nearfield, and music that is experienced as having a positive valence at a distance should be more positively......Research from animal ethology and affective neuroscience suggest that a listener’s perceived distance from a signal source can alter their experienced emotional valence of the music. Furthermore, appraisal theories of emotion suggest that emotionally valenced responses will diverge according...... to the type of emotion presented. For these exploratory investigations, subjects listen to selected musical excerpts on speakers in combination with a tactile transducer attached to their chair. The listening sessions are recorded on EEG supported by subject feedback responses. My hypothesis is that musical...

Kinetics and Mechanistic Studies on the Reaction between Cytochrome c and Tea Catechins

Directory of Open Access Journals (Sweden)

Lihua Wang

2014-08-01

Full Text Available Green tea is characterized by the presence of an abundance of polyphenolic compounds, also known as catechins, including epicatechin (EC, epigallocatechin (EGC, epicatechin gallate (EGC and epigallocatechin gallate (EGCG. In addition to being a popular beverage, tea consumption has been suggested as a mean of chemoprevention. However, its mode of action is unclear. It was discovered that tea catechins can react with cytochrome c. When oxidized cytochrome c was mixed with catechins commonly found in green tea under non-steady-state conditions, a reduction of cytochrome c was observed. The reaction rate of the catechins was dependent on the pH and the nature of the catechin. The pseudo-first order rate constant obtained increased in the order of EC < ECG < EGC < EGCG, which is consistent with previously reported superoxide reduction activities and Cu2+ reduction activities of tea catechins.

Intersite interactions and susceptibility in mixed valence systems

International Nuclear Information System (INIS)

Xiaoqian Wang; Gao Lin; Bingjian Ni; Fusui Liu.

1985-10-01

This paper considers the effect of intersite processes on the susceptibility in mixed valence system. The method of thermodynamical perturbation used in this paper can also be generalized to study other properties of mixed valence system. The general formula of partition function of two-site interactions for the mixed valence system is given. The numerical calculations show that the intersite interaction is large enough to explain the minimum of susceptibility discovered in experiments. The different types of our theoretical curves predict that the susceptibility should exhibit a rich variety of behaviour at low temperature for various materials. (author)

Space-Valence Priming with Subliminal and Supraliminal Words

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Ulrich eAnsorge

2013-02-01

Full Text Available To date it is unclear whether (1 awareness-independent non-evaluative semantic processes influence affective semantics and whether (2 awareness-independent affective semantics influence non-evaluative semantic processing. In the current study, we investigated these questions with the help of subliminal (masked primes and visible targets in a space-valence across-category congruence effect. In line with (1, we found that subliminal space prime words influenced valence classification of supraliminal target words (Experiment 1: Classifications were faster with a congruent prime (e.g., the prime ‘up’ before the target ‘happy’ than with an incongruent prime (e.g., the prime ‘up’ before the target ‘sad’. In contrast to (2, no influence of subliminal valence primes on the classification of supraliminal space targets into up- and down-words was found (Experiment 2. Control conditions showed that standard masked response-priming effects were found with both subliminal prime types, and that an across-category congruence effect was also found with supraliminal valence primes and spatial target words. The final Experiment 3 confirmed that the across-category congruence effect indeed reflected priming of target categorization of a relevant meaning category. Together, the data jointly confirmed prediction (1 that awareness-independent non-evaluative semantic priming influences valence judgments.

A numerical simulation model of valence-change-based resistive switching

OpenAIRE

Marchewka, Astrid

2017-01-01

Due to their superior scalability and performance, nanoscale resistive switches based on the valence-change mechanism are considered promising candidates for future nonvolatile memory and logic applications. These devices are metal-oxide-metal structures that can be reversibly switched between different resistance states by electrical signals. Typically, they contain one Schottky-like and one ohmic-like metal-oxide contact and exhibit bipolar switching. The switching mechanism and the initial...

Effect of valence on the electromigration in silver

International Nuclear Information System (INIS)

Nguyen Van Doan

1970-01-01

It is shown that the apparent effective valence Z B ** of a solute deduced from experiments differs from the true effective valence Z B * defined in the atomic models by a corrective term due to the 'vacancy flow effect'. The experimental results suggest that this corrective term is very important and that it is negative for transition elements; this hypothesis is confirmed for the case of iron in a copper matrix. For the elements to the right of silver in the periodic table, where the correction can be neglected, the effective valence of the solute varies linearly with z (z + 1), z being the difference between the valency of the solute and the solvent; in contrast, the further the solute is from the solvent in the periodic table the more nearly the electronic structure of the ion at the saddle point resembles that of the ion at the equilibrium position. (author) [fr

A valence-universal coupled-cluster single- and double-excitations method for atoms: Pt. 3

International Nuclear Information System (INIS)

Jankowski, K.; Malinowski, P.

1994-01-01

To better understand the problems met when solving the equations of VU-CC approaches in the presence of intruder states, we are concerned with the following aspects of the solvability problem for sets of non-linear equations: the existence and properties of multiple solutions and the attainability of these solutions by means of various numerical methods. Our study is concentrated on the equations obtained for Be within the framework of the recently formulated atomically oriented form of the valence-universal coupled-cluster theory accounting for one- and two-electron excitations (VU-CCSD/R) and based on the complete model space (2s 2 , 2p 2 ). Six pairs of multiple solutions representing four 1 S states are found and discussed. Three of these solutions provide amplitudes describing the 2p 2 1 S state for which the intruder state problem has been considered as extremely serious. Several known numerical methods have been applied to solve the same set of non-linear equations for the two-valence cluster amplitudes. It is shown that these methods perform quite differently in the presence of intruder states, which seems to indicate that the intruder state problem for VU-CC methods is partly caused by the commonly used methods of solving the non-linear equations. (author)

The acoustic correlates of valence depend on emotion family.

Science.gov (United States)

Belyk, Michel; Brown, Steven

2014-07-01

The voice expresses a wide range of emotions through modulations of acoustic parameters such as frequency and amplitude. Although the acoustics of individual emotions are well understood, attempts to describe the acoustic correlates of broad emotional categories such as valence have yielded mixed results. In the present study, we analyzed the acoustics of emotional valence for different families of emotion. We divided emotional vocalizations into "motivational," "moral," and "aesthetic" families as defined by the OCC (Ortony, Clore, and Collins) model of emotion. Subjects viewed emotional scenarios and were cued to vocalize congruent exclamations in response to them, for example, "Yay!" and "Damn!". Positive valence was weakly associated with high-pitched and loud vocalizations. However, valence interacted with emotion family for both pitch and amplitude. A general acoustic code for valence does not hold across families of emotion, whereas family-specific codes provide a more accurate description of vocal emotions. These findings are consolidated into a set of "rules of expression" relating vocal dimensions to emotion dimensions. Copyright © 2014 The Voice Foundation. Published by Mosby, Inc. All rights reserved.

Valence control of cobalt oxide thin films by annealing atmosphere

International Nuclear Information System (INIS)

Wang Shijing; Zhang Boping; Zhao Cuihua; Li Songjie; Zhang Meixia; Yan Liping

2011-01-01

The cobalt oxide (CoO and Co 3 O 4 ) thin films were successfully prepared using a spin-coating technique by a chemical solution method with CH 3 OCH 2 CH 2 OH and Co(NO 3 ) 2 .6H 2 O as starting materials. The grayish cobalt oxide films had uniform crystalline grains with less than 50 nm in diameter. The phase structure is able to tailor by controlling the annealing atmosphere and temperature, in which Co 3 O 4 thin film was obtained by annealing in air at 300-600, and N 2 at 300, and transferred to CoO thin film by raising annealing temperature in N 2 . The fitted X-ray photoelectron spectroscopy (XPS) spectra of the Co2p electrons are distinguishable from different valence states of cobalt oxide especially for their satellite structure. The valence control of cobalt oxide thin films by annealing atmosphere contributes to the tailored optical absorption property.

Sex, Age, and Emotional Valence: Revealing Possible Biases in the 'Reading the Mind in the Eyes' Task.

Science.gov (United States)

Kynast, Jana; Schroeter, Matthias L

2018-01-01

The 'Reading the Mind in the Eyes' test (RMET) assesses a specific socio-cognitive ability, i.e., the ability to identify mental states from gaze. The development of this ability in a lifespan perspective is of special interest. Whereas former investigations were limited mainly to childhood and adolescence, the focus has been shifted towards aging, and psychiatric and neurodegenerative diseases recently. Although the RMET is frequently applied in developmental psychology and clinical settings, stimulus characteristics have never been investigated with respect to potential effects on test performance. Here, we analyzed the RMET stimulus set with a special focus on interrelations between sex, age and emotional valence. Forty-three persons rated age and emotional valence of the RMET picture set. Differences in emotional valence and age ratings between male and female items were analyzed. The linear relation between age and emotional valence was tested over all items, and separately for male and female items. Male items were rated older and more negative than female stimuli. Regarding male RMET items, age predicted emotional valence: older age was associated with negative emotions. Contrary, age and valence were not linearly related in female pictures. All ratings were independent of rater characteristics. Our results demonstrate a strong confound between sex, age, and emotional valence in the RMET. Male items presented a greater variability in age ratings compared to female items. Age and emotional valence were negatively associated among male items, but no significant association was found among female stimuli. As personal attributes impact social information processing, our results may add a new perspective on the interpretation of previous findings on interindividual differences in RMET accuracy, particularly in the field of developmental psychology, and age-associated neuropsychiatric diseases. A revision of the RMET might be afforded to overcome confounds

Prediction of valence and arousal from music features

NARCIS (Netherlands)

Den Brinker, A.C.; Van Dinther, C.H.B.A.; Skowronek, J.

2011-01-01

Mood is an important attribute of music and knowledge on mood can beused as a basic ingredient in music recommender and retrieval systems. Moods are assumed to be dominantly determined by two dimensions:valence and arousal. An experiment was conducted to attain data forsong-based ratings of valence

Relaxation and cross section effects in valence band photoemission spectroscopy

International Nuclear Information System (INIS)

McFeely, F.R.

1976-09-01

Various problems relating to the interpretation of valence band x-ray photoemission (XPS) spectra of solids are discussed. The experiments and calculations reported herein deal with the following questions: (1) To what extent do many-body effects manifest themselves in an XPS valence band spectrum, and thus invalidate a direct comparison between the photoemission energy distribution, I(E), and the density of states, N(E), calculated on the basis of ground-state one-electron theory. (2) The effect of the binding-energy-dependent photoemission cross section on I(E) at XPS energies. (3) In favorable cases indicated by (1) and (2) we examine the effect of the interaction of the crystal field with the apparent spin-orbit splittings of core levels observed in XPS spectra. (4) The use of tight binding band structure calculations to parameterize the electronic band structure from XPS and other data is described. (5) The use of high energy angle-resolved photoemission on oriented single crystals to gain orbital symmetry information is discussed. (6) The evolution of the shape of the photoemission energy distribution (of polycrystalline Cu) as a function of photon energy from 50 less than or equal h ω less than or equal 175 is discussed

Valence change in rare earth semiconductors in many-impurity Anderson model

International Nuclear Information System (INIS)

Kocharyan, A.N.

1986-01-01

Green functions averaged over point impurity localization are found out in the simplest many-impurity model of rare earth semiconductor taking into account local Coulomb repulsion and hybridization of s- and f-electrons. Analytical expressions for s- and f-electron states density are obtained in the appoximation linear in can centration. Behaviour of a state density nearly the continuous spectrum edge and in the vicinity of the f-level is studied as a function of electron parameters. A comparison with the Anderson one-impurity model is performed. It is shown that essential energy spectrum conversion occurs in the case of a great number of impurities close to the continuous spectrum. Continuous spectrum boundaries are found out, and conditions are defined, at which the forbidden energy gap occurs in the continuous spectrum nearly a f-level. Effect of the coherent conversion of spectrum on behaviour of valence in changing f-level position is analyzed. It is shown that in the lack of electron-lattice interaction the phase transition with valence change occurs in a smooth manner as in the model with strictly periodic Andersen lattice

Dynamic movement of cytochrome c from mitochondria into cytosol and peripheral circulation in massive hepatic cell injury.

Science.gov (United States)

Kobayashi, Yoshinori; Mori, Masaaki; Naruto, Takuya; Kobayashi, Naoki; Sugai, Toshiyuki; Imagawa, Tomoyuki; Yokota, Shumpei

2004-12-01

In the process of apoptosis, it is known that the transition of cytochrome c from mitochondria into the cytosol occurs, and tumor necrosis factor (TNF)-alpha is one of the molecules responsible for this event. But in the state of hypercytokine induced by D-galactosamine (D-GaIN)/Lipopolysaccharide (LPS), the localization of cytochrome c is little known. Rats were administrated with D-GaIN(700 mg/kg)/LPS(200 microg/kg). Blood and tissue samples were collected and examined for levels of pro-inflammatory cytokines, the apoptosis of liver cells, and the localization of cytochrome c. Before administration of D-GaIN/LPS, cytochrome c was definitely localized in the mitochondria. At 2 h after simultaneous administration of D-GaIN/LPS, cytochrome c had accumulated in the cytosol following abrupt increases of plasma TNF-alpha. Massive cell destruction due to apoptosis proved by Terminal deoxynucleo-tidyl transferase-mediated dUTP nick end labeling staining was observed in liver tissue 4 h later and markedly increased levels of cytochrome c were detected in the plasma 12 h after D-GaIN/LPS administration. Liver injury induced by simultaneous administration of D-GaIN/LPS was closely associated with the production of TNF-alpha, and also with the dynamic movement of cytochrome c from the mitochondria into the cytosol, and then into the systemic circulation. The detection of plasma cytochrome c levels may be a useful clinical tool for the detection of apoptosis in vivo.

Valence QCD: Connecting QCD to the quark model

International Nuclear Information System (INIS)

Liu, K.F.; Dong, S.J.; Draper, T.; Sloan, J.; Leinweber, D.; Woloshyn, R.M.

1999-01-01

A valence QCD theory is developed to study the valence quark properties of hadrons. To keep only the valence degrees of freedom, the pair creation through the Z graphs is deleted in the connected insertions, whereas the sea quarks are eliminated in the disconnected insertions. This is achieved with a new 'valence QCD' Lagrangian where the action in the time direction is modified so that the particle and antiparticle decouple. It is shown in this valence version of QCD that the ratios of isovector to isoscalar matrix elements (e.g., F A /D A and F S /D S ratios) in the nucleon reproduce the SU(6) quark model predictions in a lattice QCD calculation. We also consider how the hadron masses are affected on the lattice and discover new insights into the origin of dynamical mass generation. It is found that, within statistical errors, the nucleon and the Δ become degenerate for the quark masses we have studied (ranging from 1 to 4 times the strange mass). The π and ρ become nearly degenerate in this range. It is shown that valence QCD has the C, P, T symmetries. The lattice version is reflection positive. It also has the vector and axial symmetries. The latter leads to a modified partially conserved axial Ward identity. As a result, the theory has a U(2N F ) symmetry in the particle-antiparticle space. Through lattice simulation, it appears that this is dynamically broken down to U q (N F )xU bar q (N F ). Furthermore, the lattice simulation reveals spin degeneracy in the hadron masses and various matrix elements. This leads to an approximate U q (2N F )xU bar q (2N F ) symmetry which is the basis for the valence quark model. In addition, we find that the masses of N, Δ,ρ,π,a 1 , and a 0 all drop precipitously compared to their counterparts in the quenched QCD calculation. This is interpreted as due to the disappearance of the 'constituent' quark mass which is dynamically generated through tadpole diagrams. The origin of the hyperfine splitting in the baryon is

Processing negative valence of word pairs that include a positive word.

Science.gov (United States)

Itkes, Oksana; Mashal, Nira

2016-09-01

Previous research has suggested that cognitive performance is interrupted by negative relative to neutral or positive stimuli. We examined whether negative valence affects performance at the word or phrase level. Participants performed a semantic decision task on word pairs that included either a negative or a positive target word. In Experiment 1, the valence of the target word was congruent with the overall valence conveyed by the word pair (e.g., fat kid). As expected, response times were slower in the negative condition relative to the positive condition. Experiment 2 included target words that were incongruent with the overall valence of the word pair (e.g., fat salary). Response times were longer for word pairs whose overall valence was negative relative to positive, even though these word pairs included a positive word. Our findings support the Cognitive Primacy Hypothesis, according to which emotional valence is extracted after conceptual processing is complete.

Quantum electrodynamic corrections for the valence shell in heavy many-electron atoms

International Nuclear Information System (INIS)

Thierfelder, C.; Schwerdtfeger, P.

2010-01-01

We present quantum electrodynamic (QED) calculations within the picture of bound-state QED for the frequency-dependent Breit interaction between electrons, the vacuum polarization, and the electron self-energy correction starting from the Dirac-Coulomb Hamiltonian for the ionization potentials of the group 1, 2, 11, 12, 13, and 18 elements of the periodic table, and down to the superheavy elements up to nuclear charge Z=120. The results for the s-block elements are in very good agreement with earlier studies by Labzowsky et al. [Phys. Rev. A 59, 2707 (1999)]. We discuss the influence of the variational versus perturbative treatment of the Breit interaction for valence-space ionization potentials. We argue that the lowest-order QED contributions become as important as the Breit interaction for ionization potentials out of the valence s shell.

Cytochrome c biosensor for determination of trace levels of cyanide and arsenic compounds

International Nuclear Information System (INIS)

Fuku, Xolile; Iftikar, Faiza; Hess, Euodia; Iwuoha, Emmanuel; Baker, Priscilla

2012-01-01

Highlights: ► Cytochrome c biosensor for detection of KCN, As 2 O 3 and Fe 2 K (CN) was constructed. ► Detection limits in the range of 4.3–9.1 μM for the analytes were obtained using CV, SWV and EIS. ► The detection limits for the biosensor were significantly lower than current EPA and WHO guidelines. - Abstract: An electrochemical method based on a cytochrome c biosensor was developed, for the detection of selected arsenic and cyanide compounds. Boron doped diamond (BDD) electrode was used as a transducer, onto which cytochrome c was immobilised and used for direct determination of Prussian blue, potassium cyanide and arsenic trioxide. The sensitivity as calculated from cyclic voltammetry (CV) and square wave voltammetry (SWV), for each analyte in phosphate buffer (pH = 7) was found to be in the range of (1.1–4.5) × 10 −8 A μM −1 and the detection limits ranged from 4.3 to 9.1 μM. The biosensor is therefore able to measure significantly lower than current Environmental Protection Agency (EPA) and World Health Organisation (WHO) guidelines, for these types of analytes. The protein binding was monitored as a decrease in biosensor peak currents by SWV and as an increase in biosensor charge transfer resistance by electrochemical impedance spectroscopy (EIS). EIS provided evidence that the electrocatalytic advantage of BDD electrode was not lost upon immobilisation of cytochrome c. The interfacial kinetics of the biosensor was modelled as equivalent electrical circuit based on electrochemical impedance spectroscopy data. UV–vis spectroscopy was used to confirm the binding of the protein in solution by monitoring the intensity of the soret bands and the Q bands. FTIR was used to characterise the protein in the immobilised state and to confirm that the protein was not denatured upon binding to the pre-treated bare BDD electrode. SNFTIR of cyt c immobilised at platinum electrode, was used to study the effect of oxidation state on the surface bond

Drug metabolism by cytochrome p450 enzymes: what distinguishes the pathways leading to substrate hydroxylation over desaturation?

Science.gov (United States)

Ji, Li; Faponle, Abayomi S; Quesne, Matthew G; Sainna, Mala A; Zhang, Jing; Franke, Alicja; Kumar, Devesh; van Eldik, Rudi; Liu, Weiping; de Visser, Sam P

2015-06-15

Cytochrome P450 enzymes are highly versatile biological catalysts in our body that react with a broad range of substrates. Key functions in the liver include the metabolism of drugs and xenobiotics. One particular metabolic pathway that is poorly understood relates to the P450 activation of aliphatic groups leading to either hydroxylation or desaturation pathways. A DFT and QM/MM study has been carried out on the factors that determine the regioselectivity of aliphatic hydroxylation over desaturation of compounds by P450 isozymes. The calculations establish multistate reactivity patterns, whereby the product distributions differ on each of the spin-state surfaces; hence spin-selective product formation was found. The electronic and thermochemical factors that determine the bifurcation pathways were analysed and a model that predicts the regioselectivity of aliphatic hydroxylation over desaturation pathways was established from valence bond and molecular orbital theories. Thus, the difference in energy of the OH versus the OC bond formed and the π-conjugation energy determines the degree of desaturation products. In addition, environmental effects of the substrate binding pocket that affect the regioselectivities were identified. These studies imply that bioengineering P450 isozymes for desaturation reactions will have to include modifications in the substrate binding pocket to restrict the hydroxylation rebound reaction. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reducing the negative valence of stressful memories through emotionally valenced, modality-specific tasks

NARCIS (Netherlands)

Tadmor, Avia; McNally, Richard J; Engelhard, Iris M

2016-01-01

BACKGROUND AND OBJECTIVES: People who perform a cognitively demanding secondary task while recalling a distressing memory often experience the memory as less emotional, vivid, or accurate during subsequent recollections. In this experiment, we tested whether the emotional valence (positive versus

Photoionization cross-sections of ground and excited valence levels of actinides

Directory of Open Access Journals (Sweden)

Yarzhemsky Victor G.

2012-01-01

Full Text Available The photoionization cross-sections of ground and excited atomic states of actinide atoms were calculated by the Dirac-Fock-Slater method for two excitation energies of X-ray radiation (1253.6 eV and 1486.6 eV. These data are required for calculations of intensities of X-ray photoelectron spectra of actinide compound valence bands and interpretation of experimental spectra.

Explaining the effect of event valence on unrealistic optimism.

Science.gov (United States)

Gold, Ron S; Brown, Mark G

2009-05-01

People typically exhibit 'unrealistic optimism' (UO): they believe they have a lower chance of experiencing negative events and a higher chance of experiencing positive events than does the average person. UO has been found to be greater for negative than positive events. This 'valence effect' has been explained in terms of motivational processes. An alternative explanation is provided by the 'numerosity model', which views the valence effect simply as a by-product of a tendency for likelihood estimates pertaining to the average member of a group to increase with the size of the group. Predictions made by the numerosity model were tested in two studies. In each, UO for a single event was assessed. In Study 1 (n = 115 students), valence was manipulated by framing the event either negatively or positively, and participants estimated their own likelihood and that of the average student at their university. In Study 2 (n = 139 students), valence was again manipulated and participants again estimated their own likelihood; additionally, group size was manipulated by having participants estimate the likelihood of the average student in a small, medium-sized, or large group. In each study, the valence effect was found, but was due to an effect on estimates of own likelihood, not the average person's likelihood. In Study 2, valence did not interact with group size. The findings contradict the numerosity model, but are in accord with the motivational explanation. Implications for health education are discussed.

Biogenesis of the yeast cytochrome bc1 complex.

Science.gov (United States)

Zara, Vincenzo; Conte, Laura; Trumpower, Bernard L

2009-01-01

The mitochondrial respiratory chain is composed of four different protein complexes that cooperate in electron transfer and proton pumping across the inner mitochondrial membrane. The cytochrome bc1 complex, or complex III, is a component of the mitochondrial respiratory chain. This review will focus on the biogenesis of the bc1 complex in the mitochondria of the yeast Saccharomyces cerevisiae. In wild type yeast mitochondrial membranes the major part of the cytochrome bc1 complex was found in association with one or two copies of the cytochrome c oxidase complex. The analysis of several yeast mutant strains in which single genes or pairs of genes encoding bc1 subunits had been deleted revealed the presence of a common set of bc1 sub-complexes. These sub-complexes are represented by the central core of the bc1 complex, consisting of cytochrome b bound to subunit 7 and subunit 8, by the two core proteins associated with each other, by the Rieske protein associated with subunit 9, and by those deriving from the unexpected interaction of each of the two core proteins with cytochrome c1. Furthermore, a higher molecular mass sub-complex is that composed of cytochrome b, cytochrome c1, core protein 1 and 2, subunit 6, subunit 7 and subunit 8. The identification and characterization of all these sub-complexes may help in defining the steps and the molecular events leading to bc1 assembly in yeast mitochondria.

Valence bond model potential energy surface for H4

International Nuclear Information System (INIS)

Silver, D.M.; Brown, N.J.

1980-01-01

Potential energy surfaces for the H 4 system are derived using the valence bond procedure. An ab initio evaluation of the valence bond energy expression is described and some of its numerical properties are given. Next, four semiempirical evaluations of the valence bond energy are defined and parametrized to yield reasonable agreement with various ab initio calculations of H 4 energies. Characteristics of these four H 4 surfaces are described by means of tabulated energy minima and equipotential contour maps for selected geometrical arrangements of the four nuclei

In-medium pion valence distributions in a light-front model

Energy Technology Data Exchange (ETDEWEB)

Melo, J.P.B.C. de, E-mail: joao.mello@cruzeirodosul.edu.br [Laboratório de Física Teórica e Computacional – LFTC, Universidade Cruzeiro do Sul, 01506-000 São Paulo (Brazil); Tsushima, K. [Laboratório de Física Teórica e Computacional – LFTC, Universidade Cruzeiro do Sul, 01506-000 São Paulo (Brazil); Ahmed, I. [Laboratório de Física Teórica e Computacional – LFTC, Universidade Cruzeiro do Sul, 01506-000 São Paulo (Brazil); National Center for Physics, Quaidi-i-Azam University Campus, Islamabad 45320 (Pakistan)

2017-03-10

Pion valence distributions in nuclear medium and vacuum are studied in a light-front constituent quark model. The in-medium input for studying the pion properties is calculated by the quark-meson coupling model. We find that the in-medium pion valence distribution, as well as the in-medium pion valence wave function, are substantially modified at normal nuclear matter density, due to the reduction in the pion decay constant.

Electron momentum distributions and binding energies for the valence orbitals of hydrogen bromide and hydrogen iodide

International Nuclear Information System (INIS)

Brion, C.E.; McCarthy, I.E.; Suzuki, I.H.; Weigold, E.; Williams, G.R.J.; Bedford, K.L.; Kunz, A.B.; Weidman, R.

1981-12-01

The electron binding energy spectra and momentum distributions have been obtained for the valence orbitals of HBr and HI using noncoplanar symmetric electron coincidence spectroscopy at 1200eV. The weakly bonding inner valence ns orbitals, which have not been previously observed, have their spectroscopic (pole) strength severely split among a number of ion states. For HBr the strength of the main inner valence (ns) transition is 0.42 0.03 whereas for HI it is 0.37 0.04, in close agreement with that observed for the valence s orbitals of the corresponding isoelectronic inert gas atoms. The spectroscopic strength for the two outermost orbitals is found to be close to unity, in agreement with many body Green's function calculations. The measured momentum distributions are compared with several spherically averaged MO momentum distributions, as well as (for HBr) with a Green's function calculation of the generalized overlap amplitude (GOA). The GOA momentum distributions are in excellent agreement with the HBr data, both in shape and relative magnitude. Not all of the MO momentum distributions are in reasonable agreement with the data. Comparison is also made with the calculated momentum distributions for Kr, Br, Xe and I

Probing cytochrome c in living mitochondria with surface-enhanced Raman spectroscopy

DEFF Research Database (Denmark)

Brazhe, Nadezda A.; Evlyukhin, Andrey B.; Goodilin, Eugene A.

2015-01-01

Selective study of the electron transport chain components in living mitochondria is essential for fundamental biophysical research and for the development of new medical diagnostic methods. However, many important details of inter- and intramembrane mitochondrial processes have remained in shadow...... due to the lack of non-invasive techniques. Here we suggest a novel label-free approach based on the surface-enhanced Raman spectroscopy (SERS) to monitor the redox state and conformation of cytochrome c in the electron transport chain in living mitochondria. We demonstrate that SERS spectra of living...... mitochondria placed on hierarchically structured silver-ring substrates provide exclusive information about cytochrome c behavior under modulation of inner mitochondrial membrane potential, proton gradient and the activity of ATP-synthetase. Mathematical simulation explains the observed enhancement of Raman...

Sex, Age, and Emotional Valence: Revealing Possible Biases in the ‘Reading the Mind in the Eyes’ Task

Directory of Open Access Journals (Sweden)

Jana Kynast

2018-04-01

Full Text Available The ‘Reading the Mind in the Eyes’ test (RMET assesses a specific socio-cognitive ability, i.e., the ability to identify mental states from gaze. The development of this ability in a lifespan perspective is of special interest. Whereas former investigations were limited mainly to childhood and adolescence, the focus has been shifted towards aging, and psychiatric and neurodegenerative diseases recently. Although the RMET is frequently applied in developmental psychology and clinical settings, stimulus characteristics have never been investigated with respect to potential effects on test performance. Here, we analyzed the RMET stimulus set with a special focus on interrelations between sex, age and emotional valence. Forty-three persons rated age and emotional valence of the RMET picture set. Differences in emotional valence and age ratings between male and female items were analyzed. The linear relation between age and emotional valence was tested over all items, and separately for male and female items. Male items were rated older and more negative than female stimuli. Regarding male RMET items, age predicted emotional valence: older age was associated with negative emotions. Contrary, age and valence were not linearly related in female pictures. All ratings were independent of rater characteristics. Our results demonstrate a strong confound between sex, age, and emotional valence in the RMET. Male items presented a greater variability in age ratings compared to female items. Age and emotional valence were negatively associated among male items, but no significant association was found among female stimuli. As personal attributes impact social information processing, our results may add a new perspective on the interpretation of previous findings on interindividual differences in RMET accuracy, particularly in the field of developmental psychology, and age-associated neuropsychiatric diseases. A revision of the RMET might be afforded to

Sex, Age, and Emotional Valence: Revealing Possible Biases in the ‘Reading the Mind in the Eyes’ Task

Science.gov (United States)

Kynast, Jana; Schroeter, Matthias L.

2018-01-01

The ‘Reading the Mind in the Eyes’ test (RMET) assesses a specific socio-cognitive ability, i.e., the ability to identify mental states from gaze. The development of this ability in a lifespan perspective is of special interest. Whereas former investigations were limited mainly to childhood and adolescence, the focus has been shifted towards aging, and psychiatric and neurodegenerative diseases recently. Although the RMET is frequently applied in developmental psychology and clinical settings, stimulus characteristics have never been investigated with respect to potential effects on test performance. Here, we analyzed the RMET stimulus set with a special focus on interrelations between sex, age and emotional valence. Forty-three persons rated age and emotional valence of the RMET picture set. Differences in emotional valence and age ratings between male and female items were analyzed. The linear relation between age and emotional valence was tested over all items, and separately for male and female items. Male items were rated older and more negative than female stimuli. Regarding male RMET items, age predicted emotional valence: older age was associated with negative emotions. Contrary, age and valence were not linearly related in female pictures. All ratings were independent of rater characteristics. Our results demonstrate a strong confound between sex, age, and emotional valence in the RMET. Male items presented a greater variability in age ratings compared to female items. Age and emotional valence were negatively associated among male items, but no significant association was found among female stimuli. As personal attributes impact social information processing, our results may add a new perspective on the interpretation of previous findings on interindividual differences in RMET accuracy, particularly in the field of developmental psychology, and age-associated neuropsychiatric diseases. A revision of the RMET might be afforded to overcome confounds

Developmental Reversals in False Memory: Effects of Emotional Valence and Arousal

Science.gov (United States)

Brainerd, C. J.; Holliday, R. E.; Reyna, V. F.; Yang, Y.; Toglia, M. P.

2010-01-01

Do the emotional valence and arousal of events distort children's memories? Do valence and arousal modulate counterintuitive age increases in false memory? We investigated those questions in children, adolescents, and adults using the Cornell/Cortland Emotion Lists, a word list pool that induces false memories and in which valence and arousal can…

Valence universal multireference coupled cluster calculations of the properties of indium in its ground and excited states

International Nuclear Information System (INIS)

Das, Madhulita; Chaudhuri, Rajat K; Chattopadhyay, Sudip; Sinha Mahapatra, Uttam

2011-01-01

In view of its importance in high precision spectroscopy, the valence universal multireference coupled cluster (VU-MRCC) method with four-component relativistic spinors has been applied to compute ionization potential (IP) and excitation energies (EEs) of the indium atom (In I). The effect of electron correlations on the ground and excited state properties is investigated using different levels of CC approximations and basis sets. This study reveals that for a given basis, the linearized VU-MRCC method tends to underestimate the IP, EEs and other one-electron properties such as magnetic hyperfine constant (A) compared to the full blown VU-MRCC method. Our computed results have been compared with available theoretical and experimental data. The IP, EEs, A and oscillator strengths (f) determined at the VU-MRCC level are in excellent agreement with the experimental results. The properties reported here further demonstrate that a basis set with at least h-type of orbitals is ubiquitous to achieve converged results.

The cytochrome p450 homepage.

Science.gov (United States)

Nelson, David R

2009-10-01

The Cytochrome P450 Homepage is a universal resource for nomenclature and sequence information on cytochrome P450 ( CYP ) genes. The site has been in continuous operation since February 1995. Currently, naming information for 11,512 CYPs are available on the web pages. The P450 sequences are manually curated by David Nelson, and the nomenclature system conforms to an evolutionary scheme such that members of CYP families and subfamilies share common ancestors. The organisation and content of the Homepage are described.

Spin-dependent electron-phonon coupling in the valence band of single-layer WS₂

DEFF Research Database (Denmark)

Hinsche, Nicki Frank; Ngankeu, Arlette S.; Guilloy, Kevin

2017-01-01

The absence of inversion symmetry leads to a strong spin-orbit splitting of the upper valence band of semiconducting single-layer transition-metal dichalchogenides such as MoS2 or WS2. This permits a direct comparison of the electron-phonon coupling strength in states that only differ by their spin....... Here, the electron-phonon coupling in the valence band maximum of single-layer WS2 is studied by first-principles calculations and angle-resolved photoemission. The coupling strength is found to be drastically different for the two spin-split branches, with calculated values of λK=0.0021 and 0.......40 for the upper and lower spin-split valence band of the freestanding layer, respectively. This difference is somewhat reduced when including scattering processes involving the Au(111) substrate present in the experiment but it remains significant, in good agreement with the experimental results....

Bond-Valence Constraints on Liquid Water Structure

International Nuclear Information System (INIS)

Bickmore, Barry R.; Rosso, Kevin M.; Brown, I. David; Kerisit, Sebastien N.

2009-01-01

The recent controversy about the structure of liquid water pits a new model involving water molecules in relatively stable rings-and-chains structures against the standard model that posits water molecules in distorted tetrahedral coordination. Molecular dynamics (MD) simulations 'both classical and ab initio' almost uniformly support the standard model, but since none of them can yet reproduce all the anomalous properties of water, they leave room for doubt. We argue that it is possible to evaluate these simulations by testing them against their adherence to the bond-valence model, a well known, and quantitatively accurate, empirical summary of the behavior of atoms in the bonded networks of inorganic solids. Here we use the results of ab initio molecular dynamics simulations of ice, water, and several solvated aqueous species to show that the valence sum rule (the first axiom of the bond-valence model,) is followed in both solid and liquid bond networks. We then test MD simulations of water, employing several popular potential models, against this criterion and the experimental O-O radial distribution function. It appears that most of those tested cannot satisfy both criteria well, except TIP4P and TIP5P. If the valence sum rule really can be applied to simulated liquid structures, then it follows that the bonding behaviors of atoms in liquids are in some ways identical to those in solids. We support this interpretation by showing that the simulations produce O-H-O geometries completely consistent with the range of geometries available in solids, and the distributions of instantaneous valence sums reaching the atoms in both the ice and liquid water simulations are essentially identical. Taken together, this is powerful evidence in favor of the standard distorted tetrahedral model of liquid water structure

Intermediate-Valence Tautomerism in Decamethylytterbocene Complexes of Methyl-Substituted Bipyridines

Energy Technology Data Exchange (ETDEWEB)

Booth, Corwin H.; Kazhdan, Daniel; Werkema, Evan L.; Walter, Marc D.; Lukens, Wayne W.; Bauer, Eric D.; Hu, Yung-Jin; Maron, Laurent; Eisenstein, Odile; Head-Gordon, Martin; Andersen, Richard A.

2011-01-25

Multiconfigurational, intermediate valent ground states are established in several methyl-substituted bipyridine complexes of bispentamethylcyclopentadienylytterbium, Cp*{sub 2} Yb(Me{sub x}-bipy). In contrast to Cp*{sub 2} Yb(bipy) and other substituted-bipy complexes, the nature of both the ground state and the first excited state are altered by changing the position of the methyl or dimethyl substitutions on the bipyridine rings. In particular, certain substitutions result in multiconfigurational, intermediate valent open-shell singlet states in both the ground state and the first excited state. These conclusions are reached after consideration of single-crystal x-ray diffraction (XRD), the temperature dependence of x-ray absorption near-edge structure (XANES), extended x-ray absorption fine-structure (EXAFS), and magnetic susceptibility data, and are supported by CASSCF-MP2 calculations. These results place the various Cp*{sub 2}Yb(bipy) complexes in a new tautomeric class, that is, intermediate-valence tautomers.

Chemical and valence reconstruction at the surface of SmB6 revealed by means of resonant soft x-ray reflectometry

Science.gov (United States)

Zabolotnyy, V. B.; Fürsich, K.; Green, R. J.; Lutz, P.; Treiber, K.; Min, Chul-Hee; Dukhnenko, A. V.; Shitsevalova, N. Y.; Filipov, V. B.; Kang, B. Y.; Cho, B. K.; Sutarto, R.; He, Feizhou; Reinert, F.; Inosov, D. S.; Hinkov, V.

2018-05-01

Samarium hexaboride (SmB6), a Kondo insulator with mixed valence, has recently attracted much attention as a possible host for correlated topological surface states. Here, we use a combination of x-ray absorption and reflectometry techniques, backed up with a theoretical model for the resonant M4 ,5 absorption edge of Sm and photoemission data, to establish laterally averaged chemical and valence depth profiles at the surface of SmB6. We show that upon cleaving, the highly polar (001) surface of SmB6 undergoes substantial chemical and valence reconstruction, resulting in boron termination and a Sm3 + dominated subsurface region. Whereas at room temperature, the reconstruction occurs on a timescale of less than 2 h, it takes about 24 h below 50 K. The boron termination is eventually established, irrespective of the initial termination. Our findings reconcile earlier depth resolved photoemission and scanning tunneling spectroscopy studies performed at different temperatures and are important for better control of surface states in this system.

CzEngVallex: a Bilingual Czech-English Valency Lexicon

Directory of Open Access Journals (Sweden)

Urešová Zdeňka

2016-04-01

Full Text Available This paper introduces a new bilingual Czech-English verbal valency lexicon (called CzEng-Vallex representing a relatively large empirical database. It includes 20,835 aligned valency frame pairs (i.e., verb senses which are translations of each other and their aligned arguments. This new lexicon uses data from the Prague Czech-English Dependency Treebank and also takes advantage of the existing valency lexicons for both languages: the PDT-Vallex for Czech and the EngVallex for English. The CzEngVallex is available for browsing as well as for download in the LINDAT/CLARIN repository.

Cytochrome c6B of Synechococcus sp. WH 8102 – Crystal structure and basic properties of novel c6-like family representative

International Nuclear Information System (INIS)

Zatwarnicki, Pawel; Barciszewski, Jakub; Krzywda, Szymon; Jaskolski, Mariusz; Kolesinski, Piotr; Szczepaniak, Andrzej

2014-01-01

Highlights: • Crystal structure of cytochrome c 6B from Synechococcus sp. WH 8102 was solved. • Basic biophysical properties of cytochrome c 6B were determined. • Cytochrome c 6B exhibits similar architecture to cytochrome c 6 . • Organization of heme binding pocket of cytochrome c 6B differs from that of c 6 . • Midpoint potential of cytochrome c 6B is significantly lower than of cytochrome c 6 . - Abstract: Cytochromes c are soluble electron carriers of relatively low molecular weight, containing single heme moiety. In cyanobacteria cytochrome c 6 participates in electron transfer from cytochrome b 6 f complex to photosystem I. Recent phylogenetic analysis revealed the existence of a few families of proteins homologous to the previously mentioned. Cytochrome c 6A from Arabidopsis thaliana was identified as a protein responsible for disulfide bond formation in response to intracellular redox state changes and c 550 is well known element of photosystem II. However, function of cytochromes marked as c 6B , c 6C and c M as well as the physiological process in which they take a part still remain unidentified. Here we present the first structural and biophysical analysis of cytochrome from the c 6B family from mesophilic cyanobacteria Synechococcus sp. WH 8102. Purified protein was crystallized and its structure was refined at 1.4 Å resolution. Overall architecture of this polypeptide resembles typical I-class cytochromes c. The main features, that distinguish described protein from cytochrome c 6 , are slightly red-shifted α band of UV–Vis spectrum as well as relatively low midpoint potential (113.2 ± 2.2 mV). Although, physiological function of cytochrome c 6B has yet to be determined its properties probably exclude the participation of this protein in electron trafficking between b 6 f complex and photosystem I

THE VALENCE OF CORPUSCULAR PROTEINS.

Science.gov (United States)

Gorin, M H; Mover, L S

1942-07-20

BY THE USE OF TWO EXTREME MODELS: a hydrated sphere and an unhydrated rod the valence (net charge) of corpuscular proteins can be successfully calculated from electric mobility data by the Debye-Hückel theory (modified to include the effect of the ions in the ion atmosphere) in conjunction with the electrophoretic theory of Henry. As pointed out by Abramson, this permits a comparison with values for the valence from titration data. Electrometric titration measurements of serum albumin B (Kekwick) have been determined at several ionic strengths. These results, together with the available data in the literature for serum albumin B, egg albumin, and beta-lactoglobulin have been used to compare values for the valence calculated from measurements of titration, electrophoresis, and membrane potentials. The results indicate that the usual interpretation of titration curves is open to serious question. By extrapolation of the titration data to zero ionic strength and protein concentration, there results an "intrinsic" net charge curve describing the binding of H(+) (OH(-)) ion alone. This curve agrees closely, in each case, with values of the valence calculated from mobility data (which in turn are in close accord with those estimated from membrane potential measurements). The experimental titration curves in the presence of appreciable quantities of ions and protein deviate widely from the ideal curve. It is suggested that, under these conditions, binding of undissociated acid (base) leads to erroneous values for the net charge. This binding would not affect the electrophoretic mobility. Values of the net charge obtained by the two extreme models from electrophoretic data are in agreement within 15 to 20 per cent. The agreement between the cylindrical model and the titration data is somewhat better in each case than with the sphere; i.e., this comparison enables a choice to be made between asymmetry and hydration in the interpretation of results from sedimentation and

Kondo and mixed-valence regimes in multilevel quantum dots

International Nuclear Information System (INIS)

Chudnovskiy, A. L.; Ulloa, S. E.

2001-01-01

We investigate the dependence of the ground state of a multilevel quantum dot on the coupling to an external fermionic system and on the interactions in the dot. As the coupling to the external system increases, the rearrangement of the effective energy levels in the dot signals the transition from the Kondo regime to a mixed-valence (MV) regime. The MV regime in a two-level dot is characterized by an intrinsic mixing of the levels in the dot, resulting in nonperturbative subtunneling and supertunneling phenomena that strongly influence the Kondo effect

Fluorescence properties of valence-controlled Eu{sup 2+} and Mn{sup 2+} ions in aluminosilicate glasses

Energy Technology Data Exchange (ETDEWEB)

Van Tuyen, Ho [Duy Tan University, 3 Quang Trung, Hai Chau, Da Nang (Viet Nam); Nonaka, Takamasa; Yamanaka, Ken-ichi [Toyota Central R& D Labs., Inc., Nagakute, Aichi (Japan); Chau, Pham Minh; Quy Hai, Nguyen Thi; Quang, Vu Xuan [Duy Tan University, 3 Quang Trung, Hai Chau, Da Nang (Viet Nam); Nogami, Masayuki, E-mail: mnogami@mtj.biglobe.ne.jp [Toyota Physical and Chemical Research Institute, Nagakute, Aichi (Japan); Ton Duc Thang University, Ho Chi Minh City (Viet Nam); Duy Tan University, 3 Quang Trung, Hai Chau, Da Nang (Viet Nam)

2017-04-15

Controlling of valence states of metal ions doped in glasses has attracted considerable interest due to the possibility of looking toward optical applications. In this study, new Na{sub 2}O-Al{sub 2}O{sub 3}-SiO{sub 2} glasses were developed to dope Eu{sup 2+} and Mn{sup 2+} with well controlled valence states by heating in H{sub 2} gas atmosphere, and the changes in the valence state of doped-ions and their fluorescence properties were investigated using visible and infrared optical absorption spectroscopies, X-ray absorption fine structure spectroscopy, and fluorescence spectroscopy. Among Eu{sup 3+}, Mn{sup 3+} and Mn{sup 2+} ions incorporated in the as-prepared glasses, the Eu{sup 3+} and Mn{sup 3+} ions were reduced to Eu{sup 2+} and Mn{sup 2+} ions, respectively, by heating in H{sub 2} gas and OH bonds were concurrently formed. The fluorescence spectra of glasses heated in H{sub 2} exhibited broad emission bands at 450 and 630 nm wavelength, assigned to the Eu{sup 2+} and Mn{sup 2+}, respectively, ions, in which the fluorescence intensity at 450 nm was observed to decrease with increasing Mn{sup 2+} ion content. The increased fluorescence intensities were analyzed as the energy transfer from Eu{sup 2+} to Mn{sup 2+} ions and the energy transfer efficiency was estimated with a concentration of Eu{sup 2+}and Mn{sup 2+} ions.

Lying about the valence of affective pictures: an fMRI study.

Directory of Open Access Journals (Sweden)

Tatia M C Lee

Full Text Available The neural correlates of lying about affective information were studied using a functional magnetic resonance imaging (fMRI methodology. Specifically, 13 healthy right-handed Chinese men were instructed to lie about the valence, positive or negative, of pictures selected from the International Affective Picture System (IAPS while their brain activity was scanned by a 3T Philip Achieva scanner. The key finding is that the neural activity associated with deception is valence-related. Comparing to telling the truth, deception about the valence of the affectively positive pictures was associated with activity in the inferior frontal, cingulate, inferior parietal, precuneus, and middle temporal regions. Lying about the valence of the affectively negative pictures, on the other hand, was associated with activity in the orbital and medial frontal regions. While a clear valence-related effect on deception was observed, common neural regions were also recruited for the process of deception about the valence of the affective pictures. These regions included the lateral prefrontal and inferior parietal regions. Activity in these regions has been widely reported in fMRI studies on deception using affectively-neutral stimuli. The findings of this study reveal the effect of valence on the neural activity associated with deception. Furthermore, the data also help to illustrate the complexity of the neural mechanisms underlying deception.

Hydrogen/deuterium exchange of multiply-protonated cytochrome c ions

International Nuclear Information System (INIS)

Wood, T.D.; Guan, Ziqiang; O'Connor, P.B.

1995-01-01

Low resolution measurements show gaseous multiply-protonated cytochrome c ions undergo hydrogen/deuterium (H/D) exchange with pseudo first-order kinetics at three distinct exchange levels, suggesting the co-existence of gaseous protein conformations. Although exchange levels first increase with increasing charge values, they decrease at the highest charge values, consistent with solution-phase behavior of cytochrome c, where the native structure unfolds with decreasing pH until folding into a compact A-state at lowest pH. High resolution measurements indicate the presence of at least six H/D exchange levels. Infrared (IR) laser heating and fast collisions via quadrupolar excitation (QE) increase H/D exchange levels (unfolding) while charge-stripping ions to lower charge values can increase or decrease H/D exchange levels (unfolding or folding). Wolynes has suggested studying proteins in vacuo could play an important role in delineating the contributions various forces play in the protein folding process, provided appropriate comparisons can be made between gas-phase and solution-phase structures

5th International Conference on Valence Fluctuations

CERN Document Server

Malik, S

1987-01-01

During the Koln meeting (August 28-31, 1984), Irdia was chosen as the venue for the next International Conference on Valence Fluctuations. lhis was in recognition ard appreciation of the work done, both experimental ard theoretical, by the Irdian scientists in this area during the last decade. We decided to hold this Conference in the month of January, 1987 at Bangalore. lhe subject of Valence Fluctuations has kept itself alive ard active as it has provided many shocks ard suprises particularly among the Ce- ard U-based intermetallies. lhe richness of many interesting physical phenomena occurring in mixed valent materials, the flexibility of modifying their physical properties (by alloying, for example) ard the possibility of synthesizing a wide variety of new such materials seem to be the key factors in this regard. Barely six months before this Conference, an International Conference on Anomalous Rare Earths and Actinides (ICAREA) had been held at Grenoble (July, 1986) which also focussed on mixed valence a...

Valence control of cobalt oxide thin films by annealing atmosphere

Energy Technology Data Exchange (ETDEWEB)

Wang Shijing [School of Materials Science and Engineering, University of Science and Technology Beijing, No. 30 Xueyuan Road, Beijing 100083 (China); Zhang Boping, E-mail: bpzhang@ustb.edu.cn [School of Materials Science and Engineering, University of Science and Technology Beijing, No. 30 Xueyuan Road, Beijing 100083 (China); Zhao Cuihua; Li Songjie; Zhang Meixia; Yan Liping [School of Materials Science and Engineering, University of Science and Technology Beijing, No. 30 Xueyuan Road, Beijing 100083 (China)

2011-02-01

The cobalt oxide (CoO and Co{sub 3}O{sub 4}) thin films were successfully prepared using a spin-coating technique by a chemical solution method with CH{sub 3}OCH{sub 2}CH{sub 2}OH and Co(NO{sub 3}){sub 2}.6H{sub 2}O as starting materials. The grayish cobalt oxide films had uniform crystalline grains with less than 50 nm in diameter. The phase structure is able to tailor by controlling the annealing atmosphere and temperature, in which Co{sub 3}O{sub 4} thin film was obtained by annealing in air at 300-600, and N{sub 2} at 300, and transferred to CoO thin film by raising annealing temperature in N{sub 2}. The fitted X-ray photoelectron spectroscopy (XPS) spectra of the Co2p electrons are distinguishable from different valence states of cobalt oxide especially for their satellite structure. The valence control of cobalt oxide thin films by annealing atmosphere contributes to the tailored optical absorption property.

Structure and expression of cytochrome f in an Oenothera plastome mutant.

Science.gov (United States)

Johnson, E M; Sears, B B

1990-06-01

The chloroplast mutant pm7 is one of a number of mutants derived from the plastome mutator (pm) line of Oenothera hookeri, strain Johansen. Immunoblotting showed that this mutant accumulates a protein that is cross-antigenic with cytochrome f, but five kilodaltons larger than the mature wild-type protein. Since cytochrome f is known to be translated on plastid ribosomes as a precursor with an amino-terminal extension, it is proposed that the unprocessed cytochrome f precursor accumulates in pm7. In addition to this precursor-sized cytochrome f protein, some mature-sized cytochrome f was also found in the mutant plastids. The pm7 mutation is inherited in a non-Mendelian fashion; but no alterations in chloroplast DNA restriction patterns, or differences in DNA sequence in the region encoding cytochrome f, were found in a comparison of the wild-type and pm7 chloroplast DNAs. Although the mutant was capable of synthesizing heme, no covalently-bound heme, normally found associated with mature, functional, cytochrome f was detected in the mutant at sizes expected for the presumed precursor, or for mature cytochrome f. These results indicate that the aberrant accumulation of a precursor-sized cytochrome f in pm7 is not due to a lesion directly in the plastid gene encoding cytochrome f, petA, or to a deficiency in the ability of the mutant plastids to synthesize or accumulate heme.

Valence electronic properties of porphyrin derivatives.

Science.gov (United States)

Stenuit, G; Castellarin-Cudia, C; Plekan, O; Feyer, V; Prince, K C; Goldoni, A; Umari, P

2010-09-28

We present a combined experimental and theoretical investigation of the valence electronic structure of porphyrin-derived molecules. The valence photoemission spectra of the free-base tetraphenylporphyrin and of the octaethylporphyrin molecule were measured using synchrotron radiation and compared with theoretical spectra calculated using the GW method and the density-functional method within the generalized gradient approximation. Only the GW results could reproduce the experimental data. We found that the contribution to the orbital energies due to electronic correlations has the same linear behavior in both molecules, with larger deviations in the vicinity of the HOMO level. This shows the importance of adequate treatment of electronic correlations in these organic systems.

Mechanistic Scrutiny Identifies a Kinetic Role for Cytochrome b5 Regulation of Human Cytochrome P450c17 (CYP17A1, P450 17A1.

Directory of Open Access Journals (Sweden)

Alexandr N Simonov

Full Text Available Cytochrome P450c17 (P450 17A1, CYP17A1 is a critical enzyme in the synthesis of androgens and is now a target enzyme for the treatment of prostate cancer. Cytochrome P450c17 can exhibit either one or two physiological enzymatic activities differentially regulated by cytochrome b5. How this is achieved remains unknown. Here, comprehensive in silico, in vivo and in vitro analyses were undertaken. Fluorescence Resonance Energy Transfer analysis showed close interactions within living cells between cytochrome P450c17 and cytochrome b5. In silico modeling identified the sites of interaction and confirmed that E48 and E49 residues in cytochrome b5 are essential for activity. Quartz crystal microbalance studies identified specific protein-protein interactions in a lipid membrane. Voltammetric analysis revealed that the wild type cytochrome b5, but not a mutated, E48G/E49G cyt b5, altered the kinetics of electron transfer between the electrode and the P450c17. We conclude that cytochrome b5 can influence the electronic conductivity of cytochrome P450c17 via allosteric, protein-protein interactions.

Oxygen consumption and cytochrome exidase activity of axolotl limbs muscle tissue in restoration of regenerative ability suprressed by X-irradiation

International Nuclear Information System (INIS)

Teplits, N.A.

1975-01-01

The rate of oxygen use and activity of cytochrome oxidase in a homogenate of mitochondria and nuclei of muscle tissue of axolotl limbs after suppression of their regenerative capability by x irradiation and their restoration was studied experimentally. With suppression of the regenative capability the use of oxygen was depressed. Cytochrome oxidase activity in the homogenate and mitochondria decreased compared to that of the intact limb, in the nuclei of muscle tissue it was the same or greater. With restoration of the regenerative capability of the limbs the respiration rate of the homogenate and the mitochondria increased, accompanied by increased cytochrome oxidase activity. In the nuclei the cytochrome oxidase activity did not change in the blastema stage and sharply decreased in the limb formation state. (E.T.)

Oxygen consumption and cytochrome exidase activity of axolotl limbs muscle tissue in restoration of regenerative ability suppressed by X-irradiation

Energy Technology Data Exchange (ETDEWEB)

Teplits, N A [AN SSSR, Moscow. Inst. Biologii Razvitiya

1975-01-01

The rate of oxygen use and activity of cytochrome oxidase in a homogenate of mitochondria and nuclei of muscle tissue of axolotl limbs after suppression of their regenerative capability by x irradiation and their restoration was studied experimentally. With suppression of the regenative capability the use of oxygen was depressed. Cytochrome oxidase activity in the homogenate and mitochondria decreased compared to that of the intact limb, in the nuclei of muscle tissue it was the same or greater. With restoration of the regenerative capability of the limbs the respiration rate of the homogenate and the mitochondria increased, accompanied by increased cytochrome oxidase activity. In the nuclei the cytochrome oxidase activity did not change in the blastema stage and sharply decreased in the limb formation state.

Biodegradation of Cosmetics Products: A Computational Study of Cytochrome P450 Metabolism of Phthalates

Directory of Open Access Journals (Sweden)

Fabián G. Cantú Reinhard

2017-11-01

Full Text Available Cytochrome P450s are a broad class of enzymes in the human body with important functions for human health, which include the metabolism and detoxification of compounds in the liver. Thus, in their catalytic cycle, the P450s form a high-valent iron(IV-oxo heme cation radical as the active species (called Compound I that reacts with substrates through oxygen atom transfer. This work discusses the possible degradation mechanisms of phthalates by cytochrome P450s in the liver, through computational modelling, using 2-ethylhexyl-phthalate as a model substrate. Phthalates are a type of compound commonly found in the environment from cosmetics usage, but their biodegradation in the liver may lead to toxic metabolites. Experimental studies revealed a multitude of products and varying product distributions among P450 isozymes. To understand the regio- and chemoselectivity of phthalate activation by P450 isozymes, we focus here on the mechanisms of phthalate activation by Compound I leading to O-dealkylation, aliphatic hydroxylation and aromatic hydroxylation processes. We set up model complexes of Compound I with the substrate and investigated the reaction mechanisms for products using the density functional theory on models and did a molecular mechanics study on enzymatic structures. The work shows that several reaction barriers in the gas-phase are close in energy, leading to a mixture of products. However, when we tried to dock the substrate into a P450 isozyme, some of the channels were inaccessible due to unfavorable substrate positions. Product distributions are discussed under various reaction conditions and rationalized with valence bond and thermodynamic models.

Multiplet effects in the electronic structure of intermediate-valence compounds

DEFF Research Database (Denmark)

Thunström, P.; Di Marco, I.; Grechnev, A.

2009-01-01

We present an implementation of the Hubbard-I approximation based on the exact solution of the atomic many-body problem incorporated in a full-potential linear muffin-tin orbital method of density-functional theory. Comparison between calculated and measured x-ray photoemission spectra reveal a g...... a good agreement for intermediate valence systems in open crystal structures such as YbInCu4, SmB6, and YbB12. Spectral features of the unoccupied states of SmB6 are predicted....

Chemical state analysis of heat-treated 6, 13-bis(triisopropylsilylethynyl) pentacene investigated by XPS valence band spectra, XANES spectra and first-principles calculation

International Nuclear Information System (INIS)

Muro, Maiko; Natsume, Yutaka; Kikuma, Jun; Setoyama, Hiroyuki

2014-01-01

X-ray photoelectron spectroscopy (XPS) valence band spectra reflect the chemical bonding states. To take this advantage, we tried to interpret experimental spectra by the occupied density of states (DOS) based on first principles calculation. In this work, we discussed XPS and X-ray Absorption Near Edge Structure (XANES) spectra of 6, 13-bis(triisopropylsilylethynyl) pentacene (TIPS-Pen), which is well known as an organic semiconductor. We studied chemical structure change of TIPS-Pen caused by heat-treatment at 300degC under nitrogen and under the air. It has been suggested that the structural change of pentacene skeleton by Diels-Alder type reaction occurs in both cases. In addition, the sample heat-treated under the air showed desorption of the isopropyl group and increase of oxygen concentration. (author)

Valence-to-core-detected X-ray absorption spectroscopy

DEFF Research Database (Denmark)

Hall, Eleanor R.; Pollock, Christopher J.; Bendix, Jesper

2014-01-01

X-ray absorption spectroscopy (XAS) can provide detailed insight into the electronic and geometric structures of transition-metal active sites in metalloproteins and chemical catalysts. However, standard XAS spectra inherently represent an average contribution from the entire coordination...... environment with limited ligand selectivity. To address this limitation, we have investigated the enhancement of XAS features using valence-to-core (VtC)-detected XAS, whereby XAS spectra are measured by monitoring fluorescence from valence-to-core X-ray emission (VtC XES) events. VtC emission corresponds...... to transitions from filled ligand orbitals to the metal 1s core hole, with distinct energetic shifts for ligands of differing ionization potentials. VtC-detected XAS data were obtained from multiple valence emission features for a series of well-characterized Mn model compounds; taken together, these data...

Field-induced valence transition in rare-earth system

International Nuclear Information System (INIS)

Chattopadhaya, A.; Ghatak, S.K.

2000-01-01

The magnetic field-induced valence transition in rare-earth compound has been examined based on a pseudospin S=1 Ising model proposed earlier for valence transition. The model includes finite mixing between two pertinent ionic configurations (magnetic and non-magnetic) separated by an energy gap and with intersite interaction between rare-earth ions. Using the mean field approximation the magnetic behaviour and the critical field (H c ) for transition are obtained as a function of energy gap and temperature. The phase boundary defined in terms of reduced field H c /H co and reduced temperature T/T v (T v being valence transition temperature in absence of field) is nearly independent of energy gap. These results are in qualitative agreement with experimental observation in Yb- and Eu-compounds

Work Valence as a Predictor of Academic Achievement in the Family Context

Science.gov (United States)

Porfeli, Erik; Ferrari, Lea; Nota, Laura

2013-01-01

This study asserts a theoretical model of academic and work socialization within the family setting. The presumed associations between parents' work valences, children's work valences and valence perceptions, and children's academic interest and achievement are tested. The results suggest that children's perceptions of parents mediate the…

Vibrational treatment of the formic acid double minimum case in valence coordinates

Science.gov (United States)

Richter, Falk; Carbonnière, P.

2018-02-01

One single full dimensional valence coordinate HCOOH ground state potential energy surface accurate for both cis and trans conformers for all levels up to 6000 cm-1 relative to trans zero point energy has been generated at CCSD(T)-F12a/aug-cc-pVTZ level. The fundamentals and a set of eigenfunctions complete up to about 3120 and 2660 cm-1 for trans- and cis-HCOOH, respectively, have been calculated and assigned using the improved relaxation method of the Heidelberg multi-configuration time-dependent Hartree package and an exact expression for the kinetic energy in valence coordinates generated by the TANA program. The calculated trans fundamental transition frequencies agree with experiment to within 5 cm-1. A few reassignments are suggested. Our results discard any cis trans delocalization effects for vibrational eigenfunctions up to 3640 cm-1 relative to trans zero point energy.

Plasmon waveguide resonance spectroscopic evidence for differential binding of oxidized and reduced rhodobacter capsulatus cytochrome c(2) to the cytochrome bc(1) complex mediated by the conformation of the rieske iron-sulfur protein

International Nuclear Information System (INIS)

Devanathan, S.; Salamon, Z.; Tollin, G.; Fitch, J.C.; Meyer, T.E.; Berry, E.A.; Cusanovich, M.A.

2007-01-01

The dissociation constants for the binding of Rhodobacter capsulatus cytochrome c2 and its K93P mutant to the cytochrome bc1 complex embedded in a phospholipid bilayer were measured by plasmon waveguide resonance spectroscopy in the presence and absence of the inhibitor stigmatellin. The reduced form of cytochrome c2 strongly binds to reduced cytochrome bc1 (Kd = 0.02 M) but binds much more weakly to the oxidized form (Kd = 3.1 M). In contrast, oxidized cytochrome c2 binds to oxidized cytochrome bc1 in a biphasic fashion with Kd values of 0.11 and 0.58 M. Such a biphasic interaction is consistent with binding to two separate sites or conformations of oxidized cytochrome c2 and/or cytochrome bc1. However, in the presence of stigmatellin, we find that oxidized cytochrome c2 binds to oxidized cytochrome bc1 in a monophasic fashion with high affinity (Kd = 0.06 M) and reduced cytochrome c2 binds less strongly (Kd = 0.11 M) but ∼30-fold more tightly than in the absence of stigmatellin. Structural studies with cytochrome bc1, with and without the inhibitor stigmatellin, have led to the proposal that the Rieske protein is mobile, moving between the cytochrome b and cytochrome c1 components during turnover. In one conformation, the Rieske protein binds near the heme of cytochrome c1, while the cytochrome c2 binding site is also near the cytochrome c1 heme but on the opposite side from the Rieske site, where cytochrome c2 cannot directly interact with Rieske. However, the inhibitor, stigmatellin, freezes the Rieske protein iron-sulfur cluster in a conformation proximal to cytochrome b and distal to cytochrome c1. We conclude from this that the dual conformation of the Rieske protein is primarily responsible for biphasic binding of oxidized cytochrome c2 to cytochrome c1. This optimizes turnover by maximizing binding of the substrate, oxidized cytochrome c2, when the iron-sulfur cluster is proximal to cytochrome b and minimizing binding of the product, reduced cytochrome c

Core and Valence Structures in K beta X-ray Emission Spectra of Chromium Materials

NARCIS (Netherlands)

Torres Deluigi, Maria; de Groot, Frank M. F.; Lopez-Diaz, Gaston; Tirao, German; Stutz, Guillermo; Riveros de la Vega, Jose

2014-01-01

We analyze the core and valence transitions in chromium in a series of materials with a number of different ligands and including the oxidation states: Cr-II, Cr-III, Cr-IV, and Cr-VI. To study the core-to-core transitions we employ the CTM4XAS program and investigate the shapes, widths,

Emotions and false memories: valence or arousal?

Science.gov (United States)

Corson, Yves; Verrier, Nadège

2007-03-01

The effects of mood on false memories have not been studied systematically until recently. Some results seem to indicate that negative mood may reduce false recall and thus suggest an influence of emotional valence on false memory. The present research tested the effects of both valence and arousal on recall and recognition and indicates that the effect is actually due to arousal. In fact, whether participants' mood is positive, negative, or neutral, false memories are significantly more frequent under conditions of high arousal than under conditions of low arousal.

Reduction of reversed micelle entrapped cytochrome c and cytochrome c3 by electrons generated by pulse radiolysis or by pyrene photoionization

International Nuclear Information System (INIS)

Vlsser, A.J.W.G.; Fendler, J.H.

1982-01-01

Horse heart cytochrome c and cytochrome c 3 , isolated from Desulfovibrio vulgaris, have been incorporated in sodium bis(2-ethylhexyl)sulfosuccinate (AOT) entrapped water pools in heptane. The absorption spectra of the cytochromes have been found to be strongly dependent on the water to AOT concentration ratios. The proteins solubilized in heptane by the AOT reversed micelles have retained their ability to mediate electron transfer. They reacted very rapidly with hydrated electrons, generated pulse radiolytically or, alternatively, formed in the laser photoionization of pyrene

Theoretical and experimental study of high-magnetic-field XMCD spectra at the L2,3 absorption edges of mixed-valence rare-earth compounds

International Nuclear Information System (INIS)

Kotani, Akio; Matsuda, Yasuhiro H; Nojiri, Hiroyuki

2009-01-01

X-ray magnetic circular dichroism(XMCD) spectra at the L 2,3 edges of mixed-valence rare-earth compounds in high magnetic fields are studied both theoretically and experimentally. The theoretical study is based on a new framework proposed recently by Kotani. The Zeeman splitting of 4f states, the mixed-valence character of 4f states, and the 4f-5d exchange interaction are incorporated into a single impurity Anderson model. New XMCD experiments in high magnetic fields up to 40 T are carried out for the mixed-valence compounds EuNi 2 (Si 0.18 Ge 0.82 ) 2 and YbInCu 4 by using a miniature pulsed magnet, which was developed recently by Matsuda et al. The XMCD data are taken at 5 K by transmission measurements for incident X-rays with ± helicities at BL39XU in SPring-8. After giving a survey on recent developments in the theory of XMCD spectra for mixed-valence Ce and Yb compounds, we calculate the XMCD spectra of YbInCu 4 at the field-induced valence transition around 32 T by applying the recent theoretical framework and by newly introducing at 32 T a discontinuous change in the Yb 4f level and that in the hybridization strength between the Yb 4f and conduction electrons. The calculated results are compared with the experimental ones.

Plastocyanin/cytochrome c6 interchange in Scenedesmus vacuolatus.

Science.gov (United States)

Miramar, M Dolores; Inda, Luis A; Saraiva, Lígia M; Peleato, M Luisa

2003-12-01

Plastocyanin and cytochrome c6 from the green alga Scenedesmus vacuolatus were immunoquantified in cells grown under different concentrations of copper and iron. Plastocyanin expression was constitutive, its synthesis was not significantly affected by iron availability, and increases with copper availability. On the contrary, cytochrome c6 synthesis is repressed by copper, and only residual amounts of the protein were detected at 0.1 micromol/L copper. Under copper deficiency, cytochrome c6 is slightly dependent on iron. In natural environments, plastocyanin seems to be the predominant electron donor to P700.

Temperature-induced valence transition in EuNi2(Si0.20Ge0.80)2 studied by hard X-ray photoemission spectroscopy

International Nuclear Information System (INIS)

Yamamoto, Kazuya; Kamakura, Nozomu; Taguchi, Munetaka; Chainani, Ashish; Takata, Yasutaka; Horiba, Koji; Shin, Shik; Ikenaga, Eiji; Mimura, Kojiro; Shiga, Masayuki; Wada, Hirofumi; Namatame, Hirofumi; Taniguchi, Masaki; Awaji, Mitsuhiro; Takeuchi, Akihisa; Nishino, Yoshinori; Miwa, Daigo; Tamasaku, Kenji; Ishikawa, Tetsuya; Kobayashi, Keisuke

2005-01-01

The temperature-induced mixed valence transition in EuNi 2 (Si 0.20 Ge 0.80 ) 2 has been investigated by hard X-ray (5940 eV) photoemission spectroscopy (HX-PES) for fractured surfaces, with a probing depth larger than 5 nm. The Eu 3d core-level states are studied below and above the critical valence transition temperature, T v = 80 K. The HX-PES spectra at 40 and 120 K show the mixed valence transition, with clear changes in the divalent and trivalent Eu 3d chemically shifted features. The Eu 3d HX-PES spectra indicate a mean valence of 2.70 ± 0.03 at 40 K which changes to 2.40 ± 0.03 at 120 K, in good accordance with the results of bulk Eu III -edge X-ray absorption spectroscopy measurements

The SMARTCyp cytochrome P450 metabolism prediction server

DEFF Research Database (Denmark)

Rydberg, Patrik; Gloriam, David Erik Immanuel; Olsen, Lars

2010-01-01

The SMARTCyp server is the first web application for site of metabolism prediction of cytochrome P450-mediated drug metabolism.......The SMARTCyp server is the first web application for site of metabolism prediction of cytochrome P450-mediated drug metabolism....

Magnetic circular dichroism studies on microsomal aryl hydrocarbon hydroxylase: comparison with cytochrome b/sub 5/ and cytochrome P-450/sub cam/

Energy Technology Data Exchange (ETDEWEB)

Vickery, L; Salmon, A; Sauer, K

1975-01-01

Magnetic circular dichroism spectra are reported for the visible and near ultraviolet spectral regions of liver microsomes from dimethylbenzanthracene-treated rats. The sequential addition of NADH, dithionite, and carbon monoxide enables us to determine contributions to the magnetic circular dichroism by cytochromes b/sub 5/ and P-450, which dominate the spectra. The magnetic circular dichroism of the microsomal preparation is compared with that of purified oxidized and reduced cytochrome b/sub 5/ from pig liver and with the camphor-complexed and camphor-free oxidized, reduced, and reduced carbonmonoxy cytochrome P-450/sub cam/ from Pseudomonas putida. The magnetic circular dichroism spectra of the membrane bound cytochrome b/sub 5/ are similar to those of the purified protein, indicating that little or no alteration in the environment of the heme occurs during the isolation procedure. The soluble bacterial cytochrome P-450/sub cam/ also appears to be a suitable model for microsomal P-450, although differences in the magnetic circular dichroism intensity are observed for the two enzymes. No effect of dimethylbenzanthracene on the magnetic circular dichroism spectra of induced compared to control rat microsomes could be observed.

Spin and spinless conductivity in polypyrrole. Evidence for mixed-valence conduction

Energy Technology Data Exchange (ETDEWEB)

Zotti, G.; Schiavon, G. (Ist. di Polarografia ed Elettrochimica Preparativa, Padova (Italy))

In situ conductivity of polypyrrole (as tosylate) as a function of oxidative doping level attains a maximum at three-quarters the total oxidation charge and the relevant in situ ESR signal corresponds to an equal concentration of spin-carrying (polaron) and spinless (bipolaron) species. Results are explained on the basis of mixed-valence conduction. Bipolaron conduction, taking the place of polaron-bipolaron conductivity at higher oxidation levels, accounts for persisting conductivity in the high-oxidation state.

Large shift and small broadening of Br2 valence band upon dimer formation with H2O: an ab initio study.

Science.gov (United States)

Franklin-Mergarejo, Ricardo; Rubayo-Soneira, Jesus; Halberstadt, Nadine; Ayed, Tahra; Bernal-Uruchurtu, Margarita I; Hernández-Lamoneda, Ramón; Janda, Kenneth C

2011-06-16

Valence electronic excitation spectra are calculated for the H(2)O···Br(2) complex using highly correlated ab initio potentials for both the ground and the valence electronic excited states and a 2-D approximation for vibrational motion. Due to the strong interaction between the O-Br and the Br-Br stretching motions, inclusion of these vibrations is the minimum necessary for the spectrum calculation. A basis set calculation is performed to determine the vibrational wave functions for the ground electronic state and a wave packet simulation is conducted for the nuclear dynamics on the excited state surfaces. The effects of both the spin-orbit interaction and temperature on the spectra are explored. The interaction of Br(2) with a single water molecule induces nearly as large a shift in the spectrum as is observed for an aqueous solution. In contrast, complex formation has a remarkably small effect on the T = 0 K width of the valence bands due to the fast dissociation of the dihalogen bond upon excitation. We therefore conclude that the widths of the spectra in aqueous solution are mostly due to inhomogeneous broadening. © 2011 American Chemical Society

Developmental Reversals in False Memory: Effects of Emotional Valence and Arousal

OpenAIRE

Brainerd, C. J.; Holliday, R. E.; Reyna, V. F.; Yang, Y.; Toglia, M. P.

2010-01-01

Do the emotional valence and arousal of events distort children’s memories? Do valence and arousal modulate counterintuitive age increases in false memory? We investigated those questions in children, adolescents, and adults using the Cornell/Cortland Emotion Lists, a word list pool that induces false memories and in which valence and arousal can be manipulated factorially. False memories increased with age for unpresented semantic associates of word lists, and net accuracy (the ratio of true...

Effect of temperature on the valency bands of HDO in water in the liquid and solid states. Effects on the analysis of heavy water using infra-red absorption; Effet de temperature sur les bandes de valence de HDO dans l'eau a l'etat liquide et a l'etat solide - consequences pour l'analyse de l'eau lourde par absorption infra-rouge

Energy Technology Data Exchange (ETDEWEB)

Ceccaldi, M [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

1964-07-01

After, a description of the technique used, a qualitative examination is made of the influence of the temperature on the {nu}{sub OH}(3,400 cm{sup -1}) and {nu}{sub OD} (2,500 cm{sup -1}) valence bands of HDO in the liquid state and then during the passage to the solid state. Quantitative examination with two cells of different thickness makes it possible to define the influence of temperature on the residual absorption of the pure liquid (D{sub 2}O or H{sub 2}O and on the valency bands ({nu}{sub OH} and {nu}{sub OD} respectively). It is found that a similar change occurs in the two bands but that the changes in the background are very different. During the passage from the liquid to the solid state the shape of the bands varies considerably but little change occurs in the total intensity. It has been possible to express these results in a simple form which is directly applicable to analytical problems. (authors) [French] Apres un rappel de la technique utilisee, on examine qualitativement l'influence de la temperature sur les bandes de valence {nu}{sub OH} (3400 cm{sup -1}) et {nu}{sub OD} (2500 cm{sup -1}) de HDO a l'etat liquide puis le passage a l'etat solide. L'examen quantitatif, avec deux cuves d'epaisseurs differentes, permet de preciser l'influence de la temperature sur l'absorption residuelle du liquide pur (D{sub 2}O ou H{sub 2}O) et sur les bandes de valence ( {nu}{sub OH} et {nu}{sub OD} respectivement). On constate une evolution parallele de ces bandes mais un comportement tres different du fond continu. Lors du passage de l'etat liquide a l'etat solide, la forme des bandes varie considerablement mais non l'intensite totale. On a pu formuler ces resultats sous une forme simple applicable directement aux problemes analytiques. (auteurs)

Resonance Raman study on the structure of the active sites of microsomal cytochrome P-450 isozymes LM2 and LM4.

Science.gov (United States)

Hildebrandt, P; Greinert, R; Stier, A; Taniguchi, H

1989-12-08

The isozymes 2 and 4 of rabbit microsomal cytochrome P-450 (LM2, LM4) have been studied by resonance Raman spectroscopy. Based on high quality spectra, a vibrational assignment of the porphyrin modes in the frequency range between 100-1700 cm-1 is presented for different ferric states of cytochrome P-450 LM2 and LM4. The resonance Raman spectra are interpreted in terms of the spin and ligation state of the heme iron and of heme-protein interactions. While in cytochrome P-450 LM2 the six-coordinated low-spin configuration is predominantly occupied, in the isozyme LM4 the five-coordinated high-spin form is the most stable state. The different stability of these two spin configurations in LM2 and LM4 can be attributed to the structures of the active sites. In the low-spin form of the isozymes LM4 the protein matrix forces the heme into a more rigid conformation than in LM2. These steric constraints are removed upon dissociation of the sixth ligand leading to a more flexible structure of the active site in the high-spin form of the isozyme LM4. The vibrational modes of the vinyl groups were found to be characteristic markers for the specific structures of the heme pockets in both isozymes. They also respond sensitively to type-I substrate binding. While in cytochrome P-450 LM4 the occupation of the substrate-binding pocket induces conformational changes of the vinyl groups, as reflected by frequency shifts of the vinyl modes, in the LM2 isozyme the ground-state conformation of these substituents remain unaffected, suggesting that the more flexible heme pocket can accommodate substrates without imposing steric constraints on the porphyrin. The resonance Raman technique makes structural changes visible which are induced by substrate binding in addition and independent of the changes associated with the shift of the spin state equilibrium: the high-spin states in the substrate-bound and substrate-free enzyme are structurally different. The formation of the inactive form

Cytochrome b 6 f function and localization, phosphorylation state of thylakoid membrane proteins and consequences on cyclic electron flow.

Science.gov (United States)

Dumas, Louis; Chazaux, Marie; Peltier, Gilles; Johnson, Xenie; Alric, Jean

2016-09-01

Both the structure and the protein composition of thylakoid membranes have an impact on light harvesting and electron transfer in the photosynthetic chain. Thylakoid membranes form stacks and lamellae where photosystem II and photosystem I localize, respectively. Light-harvesting complexes II can be associated to either PSII or PSI depending on the redox state of the plastoquinone pool, and their distribution is governed by state transitions. Upon state transitions, the thylakoid ultrastructure and lateral distribution of proteins along the membrane are subject to significant rearrangements. In addition, quinone diffusion is limited to membrane microdomains and the cytochrome b 6 f complex localizes either to PSII-containing grana stacks or PSI-containing stroma lamellae. Here, we discuss possible similarities or differences between green algae and C3 plants on the functional consequences of such heterogeneities in the photosynthetic electron transport chain and propose a model in which quinones, accepting electrons either from PSII (linear flow) or NDH/PGR pathways (cyclic flow), represent a crucial control point. Our aim is to give an integrated description of these processes and discuss their potential roles in the balance between linear and cyclic electron flows.

Human Amygdala Tracks a Feature-Based Valence Signal Embedded within the Facial Expression of Surprise.

Science.gov (United States)

Kim, M Justin; Mattek, Alison M; Bennett, Randi H; Solomon, Kimberly M; Shin, Jin; Whalen, Paul J

2017-09-27

Human amygdala function has been traditionally associated with processing the affective valence (negative vs positive) of an emotionally charged event, especially those that signal fear or threat. However, this account of human amygdala function can be explained by alternative views, which posit that the amygdala might be tuned to either (1) general emotional arousal (activation vs deactivation) or (2) specific emotion categories (fear vs happy). Delineating the pure effects of valence independent of arousal or emotion category is a challenging task, given that these variables naturally covary under many circumstances. To circumvent this issue and test the sensitivity of the human amygdala to valence values specifically, we measured the dimension of valence within the single facial expression category of surprise. Given the inherent valence ambiguity of this category, we show that surprised expression exemplars are attributed valence and arousal values that are uniquely and naturally uncorrelated. We then present fMRI data from both sexes, showing that the amygdala tracks these consensus valence values. Finally, we provide evidence that these valence values are linked to specific visual features of the mouth region, isolating the signal by which the amygdala detects this valence information. SIGNIFICANCE STATEMENT There is an open question as to whether human amygdala function tracks the valence value of cues in the environment, as opposed to either a more general emotional arousal value or a more specific emotion category distinction. Here, we demonstrate the utility of surprised facial expressions because exemplars within this emotion category take on valence values spanning the dimension of bipolar valence (positive to negative) at a consistent level of emotional arousal. Functional neuroimaging data showed that amygdala responses tracked the valence of surprised facial expressions, unconfounded by arousal. Furthermore, a machine learning classifier identified

Effects of valence and divided attention on cognitive reappraisal processes.

Science.gov (United States)

Morris, John A; Leclerc, Christina M; Kensinger, Elizabeth A

2014-12-01

Numerous studies have investigated the neural substrates supporting cognitive reappraisal, identifying the importance of cognitive control processes implemented by prefrontal cortex (PFC). This study examined how valence and attention affect the processes used for cognitive reappraisal by asking participants to passively view or to cognitively reappraise positive and negative images with full or divided attention. When participants simply viewed these images, results revealed few effects of valence or attention. However, when participants engaged in reappraisal, there was a robust effect of valence, with the reappraisal of negative relative to positive images associated with more widespread activation, including within regions of medial and lateral PFC. There also was an effect of attention, with more lateral PFC recruitment when regulating with full attention and more medial PFC recruitment when regulating with divided attention. Within two regions of medial PFC and one region of ventrolateral PFC, there was an interaction between valence and attention: in these regions, divided attention reduced activity during reappraisal of positive but not negative images. Critically, participants continued to report reappraisal success even during the Divided Attention condition. These results suggest multiple routes to successful cognitive reappraisal, depending upon image valence and the availability of attentional resources. © The Author (2014). Published by Oxford University Press. For Permissions, please email: journals.permissions@oup.com.

Effects of valence and divided attention on cognitive reappraisal processes

Science.gov (United States)

Leclerc, Christina M.; Kensinger, Elizabeth A.

2014-01-01

Numerous studies have investigated the neural substrates supporting cognitive reappraisal, identifying the importance of cognitive control processes implemented by prefrontal cortex (PFC). This study examined how valence and attention affect the processes used for cognitive reappraisal by asking participants to passively view or to cognitively reappraise positive and negative images with full or divided attention. When participants simply viewed these images, results revealed few effects of valence or attention. However, when participants engaged in reappraisal, there was a robust effect of valence, with the reappraisal of negative relative to positive images associated with more widespread activation, including within regions of medial and lateral PFC. There also was an effect of attention, with more lateral PFC recruitment when regulating with full attention and more medial PFC recruitment when regulating with divided attention. Within two regions of medial PFC and one region of ventrolateral PFC, there was an interaction between valence and attention: in these regions, divided attention reduced activity during reappraisal of positive but not negative images. Critically, participants continued to report reappraisal success even during the Divided Attention condition. These results suggest multiple routes to successful cognitive reappraisal, depending upon image valence and the availability of attentional resources. PMID:24493837

Cytochrome P450 monooxygenases and insecticide resistance in insects.

OpenAIRE

Bergé, J B; Feyereisen, R; Amichot, M

1998-01-01

Cytochrome P450 monooxygenases are involved in many cases of resistance of insects to insecticides. Resistance has long been associated with an increase in monooxygenase activities and with an increase in cytochrome P450 content. However, this increase does not always account for all of the resistance. In Drosophila melanogaster, we have shown that the overproduction of cytochrome P450 can be lost by the fly without a corresponding complete loss of resistance. These results prompted the seque...

Memory effects of sleep, emotional valence, arousal and novelty in children.

Science.gov (United States)

Vermeulen, Marije C M; van der Heijden, Kristiaan B; Benjamins, Jeroen S; Swaab, Hanna; van Someren, Eus J W

2017-06-01

Effectiveness of memory consolidation is determined by multiple factors, including sleep after learning, emotional valence, arousal and novelty. Few studies investigated how the effect of sleep compares with (and interacts with) these other factors, of which virtually none are in children. The present study did so by repeated assessment of declarative memory in 386 children (45% boys) aged 9-11 years through an online word-pair task. Children were randomly assigned to either a morning or evening learning session of 30 unrelated word-pairs with positive, neutral or negative valenced cues and neutral targets. After immediately assessing baseline recognition, delayed recognition was recorded either 12 or 24 h later, resulting in four different assessment schedules. One week later, the procedure was repeated with exactly the same word-pairs to evaluate whether effects differed for relearning versus original novel learning. Mixed-effect logistic regression models were used to evaluate how the probability of correct recognition was affected by sleep, valence, arousal, novelty and their interactions. Both immediate and delayed recognition were worse for pairs with negatively valenced or less arousing cue words. Relearning improved immediate and delayed word-pair recognition. In contrast to these effects, sleep did not affect recognition, nor did sleep moderate the effects of arousal, valence and novelty. The findings suggest a robust inclination of children to specifically forget the pairing of words to negatively valenced cue words. In agreement with a recent meta-analysis, children seem to depend less on sleep for the consolidation of information than has been reported for adults, irrespective of the emotional valence, arousal and novelty of word-pairs. © 2017 European Sleep Research Society.

Investigating Valence and Autonomy in Children's Relationships with Imaginary Companions

Science.gov (United States)

McInnis, Melissa A.; Pierucci, Jillian M.; Gilpin, Ansley Tullos

2013-01-01

Little research has explored valence and autonomy in children's imaginary relationships. In the present study, a new interview (modeled after an existing measure for real relationships) was designed to elicit descriptions of both positive and negative interactions with imaginary companions and to provide a measure of relationship valence and…

One-electron reduction of mitomycin c by rat liver : role of cytochrome P-450 and NADPH-cytochrome P-450 reductase

NARCIS (Netherlands)

Vromans, R M; Van de Straat, R; Groeneveld, M.; Vermeulen, N P

1. The role of cytochrome P-450 in the one-electron reduction of mitomycin c was studied in rat hepatic microsomal systems and in reconstituted systems of purified cytochrome P-450. Formation of H2O2 from redox cycling of the reduced mitomycin c in the presence of O2 and the alkylation of

Negative pressure driven valence instability of Eu in cubic Eu{sub 0.4}La{sub 0.6}Pd{sub 3}

Energy Technology Data Exchange (ETDEWEB)

Pandey, Abhishek [S N Bose National Centre for Basic Sciences, Block-JD, Sector-III, Salt Lake, Kolkata-700098 (India); Mazumdar, Chandan; Ranganathan, R [Experimental Condensed Matter Physics Division, Saha Institute of Nuclear Physics, 1/AF, Bidhannagar, Kolkata-700064 (India)], E-mail: abhishek.phy@gmail.com, E-mail: chandan.mazumar@saha.ac.in

2009-05-27

We report the change in the valency of Eu-ions in the binary intermetallic cubic compound EuPd{sub 3} induced by La doping at rare-earth sites. Doping of La generates negative chemical pressure in the lattice, resulting in a significant increase of the lattice parameter without altering the simple-cubic structure of the compound. Results of dc-magnetic measurements suggest that this increase in the lattice parameter is associated with the valence transition of Eu-ions from Eu{sup 3+} to a mixed-valent state. As Eu{sup 2+}-ions possess a large magnetic moment, this valence transition significantly modifies the magnetic behavior of the compound. In contrast to introducing boron at the vacant body center site of the unit cell to change the valency of Eu-ions, as in the case of EuPd{sub 3}B, our results suggest it can also be altered by doping a rare-earth ion of larger size at the lattice site of Eu in EuPd{sub 3}.

Direct double photoionization of the valence shell of Be

International Nuclear Information System (INIS)

Citrini, F.; Malegat, L.; Selles, P.; Kazansky, A.K.

2003-01-01

The hyperspherical R-matrix method with semiclassical outgoing waves is used to study the direct double photoionization (DPI) of the valence shell of the lightest alkaline earth-metal Be. The absolute fully integrated, singly, doubly, and triply differential cross sections obtained are compared with the single set of measurements available and with recent calculations based on the convergent close coupling and time-dependent close coupling methods. The level of agreement between all these data is very encouraging. A comparison is also made between the DPI of He and the direct DPI of the valence shell of Be. It confirms that the electron-electron correlations are stronger in the valence 2s shell of Be than in the 1s shell of He, thus contributing to a desirable clarification

In vitro effects of myricetin, morin, apigenin, (+)-taxifolin, (+)-catechin, (−)-epicatechin, naringenin and naringin on cytochrome b5 reduction by purified NADH-cytochrome b5 reductase

International Nuclear Information System (INIS)

Çelik, Haydar; Koşar, Müberra; Arinç, Emel

2013-01-01

Highlights: • We assessed inhibitory effects of 8 dietary flavonoids on cytochrome b5 reduction by purified NADH-cytochrome b5 reductase. • The flavonol myricetin was the most potent in inhibiting cytochrome b5 reduction with an IC 50 value of 0.35 μM. • We investigated kinetics of myricetin-induced inhibition in detail. • We explored the structure–inhibitory activity relationship of compounds. • Modulation of cytochrome b5 reduction indicates a potential for myricetin to lead to some food–drug/xenobiotic interactions. - Abstract: The microsomal NADH-dependent electron transport system consisting of cytochrome b5 reductase and cytochrome b5 participates in a number of physiologically important processes including lipid metabolism as well as is involved in the metabolism of various drug and xenobiotics. In the present study, we assessed the inhibitory effects of eight dietary flavonoids representing five distinct chemical classes on cytochrome b5 reduction by purified cytochrome b5 reductase. From the flavonoids tested, myricetin was the most potent in inhibiting cytochrome b5 reduction with an IC 50 value of 0.35 μM. Myricetin inhibited b5 reductase noncompetitively with a K i of 0.21 μM with respect to cofactor NADH, and exhibited a non-linear relationship indicating non-Michaelis–Menten kinetic binding with respect to cytochrome b5. In contrast to the potent inhibitory activity of myricetin, (+)-taxifolin was found to be a weak inhibitor (IC 50 = 9.8 μM). The remaining flavonoids were inactive within the concentration range tested (1–50 μM). Analysis of structure–activity data suggested that simultaneous presence of three OH groups in ring B is a primary structural determinant for a potent enzyme inhibition. Our results suggest that inhibition of the activity of this system by myricetin or myricetin containing diets may influence the metabolism of therapeutic drugs as well as detoxification of xenobiotics

[ATP-synthetase activity, respiration and cytochromes of rat heart mitochondria in aging and hyperthyroidism].

Science.gov (United States)

Lemeshko, V V; Kaliman, P A; Belostotskaia, L I; Uchitel', A A

1982-04-01

The ATP-synthetase activity, the rate of oxygen uptake under different metabolic conditions, the tightness of coupling of respiration to oxidative phosphorylation and the cytochrome contents in heart mitochondria of rats from different age groups were studied under normal conditions and in hyperthyroidism. It was found that heart mitochondria of aged animals did not practically differ in terms of their functional activity from those of the young animals. Administration of thyroxin to the animals from all age groups produced no significant effects on the state of mitochondria, increasing the rate of ATP synthesis on alpha-glycerophosphate, which was especially well-pronounced in aged animals, and the cytochrome content in 1-month-old rats.

Magnetite Crisis in Miniature: Vanadium, Sulfur, and Iron Valence State Measurements in Melt Inclusions from Nyamuragira Volcano (D.R. Congo, Africa)

Science.gov (United States)

Head, E.; Lanzirotti, A.; Sutton, S.; Newville, M.

2017-12-01

Sulfur (S), vanadium (V), and iron (Fe) K-edge micro-X-ray absorption near edge structure (micro-XANES) spectroscopy of melt inclusions (MI) from Nyamuragira volcano (D.R. Congo, Africa) shows that diffusive loss of H from olivine-hosted melt inclusions may lead to crystallization of submicron magnetite and sulfide crystallites that are imperceptible petrographically or via electron microscopy. Micro-XANES was used to constrain the evolution of oxygen fugacity (fO2) and sulfur speciation for MI preserved in Nyamuragira tephra (1986 and 2006) and lava (1938 and 1948). The S, V, and Fe valence state oxybarometry for 1938, 1948, and 2006 MI are all consistent with equilibration at FMQ-1, and sulfur in MI from these three eruptions are sulfide-dominated (water loss in olivine-hosted MIs.

Effectiveness of cytochrome C and cepharanthin for leukopenia following multidisciplinary treatment

International Nuclear Information System (INIS)

Tabata, Kumiko; Endow, Masaru; Suzuki, Hirotoshi

1986-01-01

Leukopenia is one of important problems for multidisciplinary treatment of malignant tumor. We could not be able to take a continuous cancer therapy because of leukopenia. And then we had a study of effectiveness combination treatment of cytochrome C with cepharanthin for leukopenia of cancer patient. We carried on the study of 3 classifications of treatment as follows, a) cytochrome C only, b) combined cytochrome C with cepharanthin, and c) control group without drugs. Bone marrow potentiality is individual differentiation and then the group was administrated both cytochrome C and cepharanthin following radiotherapy associated with postoperative breast cancer. The above description lead to conclusion that combination treatment of cytochrome C and cepharanthin was available for protective drugs from multidisciplinary treatment induced leukemia. (author)

The reaction of neuroglobin with potential redox protein partners cytochrome b5  and cytochrome c

DEFF Research Database (Denmark)

Fago, Angela; Mathews, A.J.; Moens, L.

2006-01-01

Previously identified, potentially neuroprotective reactions of neuroglobin require the existence of yet unknown redox partners. We show here that the reduction of ferric neuroglobin by cytochrome b5 is relatively slow (k=6×102M-1s-1 at pH 7.0) and thus is unlikely to be of physiological...... significance. In contrast, the reaction between ferrous neuroglobin and ferric cytochrome c is very rapid (k=2×107M-1s-1) with an apparent overall equilibrium constant of 1μM. Based on this data we propose that ferrous neuroglobin may well play a role in preventing apoptosis...

Investigation of the redox-dependent modulation of structure and dynamics in human cytochrome c.

Science.gov (United States)

Imai, Mizue; Saio, Tomohide; Kumeta, Hiroyuki; Uchida, Takeshi; Inagaki, Fuyuhiko; Ishimori, Koichiro

2016-01-22

Redox-dependent changes in the structure and dynamics of human cytochrome c (Cyt c) were investigated by solution NMR. We found significant structural changes in several regions, including residues 23-28 (loop 3), which were further corroborated by chemical shift differences between the reduced and oxidized states of Cyt c. These differences are essential for discriminating redox states in Cyt c by cytochrome c oxidase (CcO) during electron transfer reactions. Carr-Purcell-Meiboom-Gill (CPMG) relaxation dispersion experiments identified that the region around His33 undergoes conformational exchanges on the μs-ms timescale, indicating significant redox-dependent structural changes. Because His33 is not part of the interaction site for CcO, our data suggest that the dynamic properties of the region, which is far from the interaction site for CcO, contribute to conformational changes during electron transfer to CcO. Copyright © 2015 Elsevier Inc. All rights reserved.

Momentum distributions and ionization potentials for the valence orbitals of hydrogen fluoride and hydrogen chloride

International Nuclear Information System (INIS)

Brion, C.E.; Hood, S.T.; Suzuki, I.H.; Weigold, E.

1980-02-01

The binding energy spectra and momentum distributions for the valence orbitals of HF and HCl have been obtained using (e,2e) spectroscopy with symmetric kinematics at 1200eV and 400eV. For HCl the strength of the innermost valence orbital (4sigma) is found to be significantly split among several ion states in the range 25eV to 41eV. The corresponding orbital in HF (2sigma) is however not significantly split among ion states. The measured momentum distributions are compared with the results of several calculatons of at least double zeta quality as well as with a one particle Green's function calculation of the generalized overlap amplitude. Agreement in shape is quite good for the innermost orbitals, but for the π and outer sigma orbitals of HF the momentum distributions calculated directly from the molecular orbitals are significantly more extended in momentum space than the measured distributions. The Green's function calculations give momentum distributions in good agreement with the data and pole strengths for transitions in qualitative agreement with the observed cross sections

Oxidation of tertiary amines by cytochrome p450-kinetic isotope effect as a spin-state reactivity probe.

Science.gov (United States)

Li, Chunsen; Wu, Wei; Cho, Kyung-Bin; Shaik, Sason

2009-08-24

Two types of tertiary amine oxidation processes, namely, N-dealkylation and N-oxygenation, by compound I (Cpd I) of cytochrome P450 are studied theoretically using hybrid DFT calculations. All the calculations show that both N-dealkylation and N-oxygenation of trimethylamine (TMA) proceed preferentially from the low-spin (LS) state of Cpd I. Indeed, the computed kinetic isotope effects (KIEs) for the rate-controlling hydrogen abstraction step of dealkylation show that only the KIE(LS) fits the experimental datum, whereas the corresponding value for the high-spin (HS) process is much higher. These results second those published before for N,N-dimethylaniline (DMA), and as such, they further confirm the conclusion drawn then that KIEs can be a sensitive probe of spin state reactivity. The ferric-carbinolamine of TMA decomposes most likely in a non-enzymatic reaction since the Fe-O bond dissociation energy (BDE) is negative. The computational results reveal that in the reverse reaction of N-oxygenation, the N-oxide of aromatic amine can serve as a better oxygen donor than that of aliphatic amine to generate Cpd I. This capability of the N-oxo derivatives of aromatic amines to transfer oxygen to the heme, and thereby generate Cpd I, is in good accord with experimental data previously reported.

Relation between plasmons and the valence-band density-of-states in polymethylmethacrylate - influence of ion irradiation on damage selectivity

International Nuclear Information System (INIS)

Moliton, J.P.; Jussiaux, C.; Trigaud, T.; Lazzaroni, R.; Lhost, O.; Bredas, J.L.; Kihn, Y.; Sevely, J.

1996-01-01

A physical model is presented that aims at rationalizing the selectivity of bond breakage observed when polymethylmethacrylate is irradiated by ions in the 10-500 keV energy range. This model, previously proposed by Brandt and Ritchie, is based on electronic collective effects. The coupling between the pure plasma oscillation at omega(p) and the oscillation of free electrons at [omega(k0)(2)](1/2) makes the whole electronic population resonant at the frequency omega(rp) = (omega(p)(2) + [omega(k0)(2)])(1/2). By computing the valence-band density of states, we calculate [omega(k0)(2)] and then deduce the theoretical value of omega(rp). On the other hand, we provide an experimental measurement of omega(rp) and study its dependence on ion fluence by electron-energy-loss spectroscopy. The validity of the model of Brandt and Ritchie is then discussed in the light of both theoretical and experimental data. (author)

Conformational changes of the NADPH-dependent cytochrome P450 reductase in the course of electron transfer to cytochromes P450

DEFF Research Database (Denmark)

Laursen, Tomas; Jensen, Kenneth; Møller, Birger Lindberg

2011-01-01

The NADPH-dependent cytochrome P450 reductase (CPR) is a key electron donor to eucaryotic cytochromes P450 (CYPs). CPR shuttles electrons from NADPH through the FAD and FMN-coenzymes into the iron of the prosthetic heme-group of the CYP. In the course of these electron transfer reactions, CPR und...... to serve as an effective electron transferring "nano-machine"....

RKKY interaction in mixed valence system and heavy fermion superconductivity

International Nuclear Information System (INIS)

Fusui Liu; Gao Lin; Lin Zonghan

1985-11-01

The 1-D RKKY interaction of mixed valence system is given by using the thermodynamic perturbation theory. The numerical comparisons of 1-D and 3-D RKKY interaction between systems with localized magnetic moments of mixed valence and non-mixed valence show that the former is much stronger than the latter. From some analyses we propose that the heavy Fermion superconductivity comes from the RKKY interaction between two local f electrons which hop off the impurity site to become two continuum electrons. The source of the two impurity electrons hopping is the Coulomb interaction. It is also emphasized that the RKKY interaction does not disappear for the Kondo lattice, when the temperature is less than the Kondo temperature. (author)

Versatility of non-native forms of human cytochrome c: pH and micellar concentration dependence.

Science.gov (United States)

Simon, Matthieu; Metzinger-Le Meuth, Valérie; Chevance, Soizic; Delalande, Olivier; Bondon, Arnaud

2013-01-01

In addition to its electron transfer activity, cytochrome c is now known to trigger apoptosis via peroxidase activity. This new function is related to a structural modification of the cytochrome upon association with anionic lipids, particularly cardiolipin present in the mitochondrial membrane. However, the exact nature of the non-native state induced by this interaction remains an active subject of debate. In this work, using human cytochromes c (native and two single-histidine mutants and the corresponding double mutant) and micelles as a hydrophobic medium, we succeeded, through UV-visible spectroscopy, circular dichroism spectroscopy and NMR spectroscopy, in fully characterizing the nature of the sixth ligand replacing the native methionine. Furthermore, careful pH titrations permitted the identification of the amino acids involved in the iron binding over a range of pH values. Replacement of the methionine by lysine was only observed at pH above 8.5, whereas histidine binding is dependent on both pH and micelle concentration. The pH variation range for histidine protonation is relatively narrow and is consistent with the mitochondrial intermembrane pH changes occurring during apoptosis. These results allow us to rule out lysine as the sixth ligand at pH values close to neutrality and reinforce the role of histidines (preferentially His33 vs. His26) as the main candidate to replace methionine in the non-native cytochrome c. Finally, on the basis of these results and molecular dynamics simulations, we propose a 3D model for non-native cytochrome c in a micellar environment.

Levels and transitions in /sup 204/Pb and the four valence neutron-hole configurations

International Nuclear Information System (INIS)

Hanly, J.M.; Hicks, S.E.; McEllistrem, M.T.; Yates, S.W.

1988-01-01

Levels of the nucleus /sup 204/Pb have been investigated using the (n,n'γ) reaction, and γ rays from low-spin excited levels have been observed. Forty-three low-spin levels connected by 78 γ rays are found below 2.9 MeV, whereas only about 28 levels had previously been known. The levels below 2 MeV excitation energy are expected to be dominated by the p/sub 1/2/, f/sub 5/2/, and p/sub 3/2/ valence neutron hole excitations, and 0 + levels at 0, 1730, and 2433.1 keV are associated primarily with these configurations. These states are at almost the same excitation energies as parent 0 + excitations in /sup 206/Pb. Approximately six unnatural-parity levels are identified; this is close to the number predicted in six orbit valence-space shell model calculations. The number of natural-parity levels found, however, is almost twice that calculated with the shell model. Levels and transitions below 2 MeV excitation energy are consistent with expectations basing /sup 204/Pb states on correlated two-hole excitations dominant in /sup 206/Pb

Prediction of activation energies for hydrogen abstraction by cytochrome p450

DEFF Research Database (Denmark)

Olsen, Lars; Rydberg, Patrik; Rod, Thomas Holm

2006-01-01

We have estimated the activation energy for hydrogen abstraction by compound I in cytochrome P450 for a diverse set of 24 small organic substrates using state-of-the-art density functional theory (B3LYP). We then show that these results can be reproduced by computationally less demanding methods,...... of the less demanding methods are applied to study the CYP3A4 metabolism of progesterone and dextromethorphan....

Redox active molecules cytochrome c and vitamin C enhance heme-enzyme peroxidations by serving as non-specific agents for redox relay

International Nuclear Information System (INIS)

Gade, Sudeep Kumar; Bhattacharya, Subarna; Manoj, Kelath Murali

2012-01-01

Highlights: ► At low concentrations, cytochrome c/vitamin C do not catalyze peroxidations. ► But low levels of cytochrome c/vitamin C enhance diverse heme peroxidase activities. ► Enhancement positively correlates to the concentration of peroxide in reaction. ► Reducible additives serve as non-specific agents for redox relay in the system. ► Insight into electron transfer processes in routine and oxidative-stress states. -- Abstract: We report that incorporation of very low concentrations of redox protein cytochrome c and redox active small molecule vitamin C impacted the outcome of one-electron oxidations mediated by structurally distinct plant/fungal heme peroxidases. Evidence suggests that cytochrome c and vitamin C function as a redox relay for diffusible reduced oxygen species in the reaction system, without invoking specific or affinity-based molecular interactions for electron transfers. The findings provide novel perspectives to understanding – (1) the promiscuous role of cytochrome b 5 in the metabolism mediated by liver microsomal xenobiotic metabolizing systems and (2) the roles of antioxidant molecules in affording relief from oxidative stress.

Influence of acute and chronic administration of methadone hydrochloride on NADPH-cytochrome c reductase and cytochrome P-450 of mouse liver microsomes.

Science.gov (United States)

Datta, R K; Johnson, E A; Bhattacharjee, G; Stenger, R J

1976-03-01

Administration of a single acute dose (20 mg/kg body weight) of methadone hydrochloride to both male and female mice increased the specific activity of NADPH-cytochrome c reductase and did not change much the content of cytochrome P-450 of their liver microsomes. Administration of multiple acute doses of methadone in male mice increased the specific activity of cytochrome c reductase and the content of cytochrome P-450 of their liver microsomes. Chronic administration of progressively increasing doses of methadone (up to 40 mg/kg body weight) to male mice increased the specific activity of c reductase. Similar chronic administration of methadone up to 28 mg/kg body weight also increased the microsomal content of P-450, but with higher doses of methadone, the content of P-450 declined and finally dropped slightly below control levels. The levels of c reductase activity and P-450 content returned to normal about two weeks after discontinuation of methadone administration.

Peculiarities of the intermediate valence state of Ce in CeM2Si2 (M = Fe, Co, Ni) compounds

International Nuclear Information System (INIS)

Koterlyn, M.; Shcherba, I.; Yasnitskii, R.; Koterlyn, G.

2007-01-01

The results of thermoelectric power and the electrical resistivity measurements connected with the intermediate valence (IV) of Ce are presented for the compounds CeM 2 Si 2 (M = Fe, Co, Ni) in the temperature range of 4-800 K. It is shown that CeM 2 Si 2 are Kondo-lattices with the coherence scale T coh ∼ 60-80 K and the so-called single-site Kondo temperature T K ∼ 10 3 K. On the example of CeNi 2 Si 2 we have studied the changes in the structure of density of f states (f-DOS) near the Fermi energy caused by atomic substitutions. The results of structural, transport, magnetic, and Ce L III X-ray absorption spectra measurements in the series Ce 1-x La x Ni 2 Si 2 (0 ≤ x ≤ 0.6), Ce(Ni 1-y Cu y ) 2 Si 2 (0 ≤ y ≤ 0.6) and CeNi 2 (Si 1-z Ge z ) 2 (0 ≤ z ≤ 0.5) are presented. We found that the IV state of Ce in the CeM 2 Si 2 is an evidence of possible opening a wide pseudogap Δ ∼ kT K within the f-DOS structure slightly above the Fermi energy

Microscopic theory of the nearest-neighbor valence bond sector of the spin-1/2 kagome antiferromagnet

Science.gov (United States)

Ralko, Arnaud; Mila, Frédéric; Rousochatzakis, Ioannis

2018-03-01

The spin-1/2 Heisenberg model on the kagome lattice, which is closely realized in layered Mott insulators such as ZnCu3(OH) 6Cl2 , is one of the oldest and most enigmatic spin-1/2 lattice models. While the numerical evidence has accumulated in favor of a quantum spin liquid, the debate is still open as to whether it is a Z2 spin liquid with very short-range correlations (some kind of resonating valence bond spin liquid), or an algebraic spin liquid with power-law correlations. To address this issue, we have pushed the program started by Rokhsar and Kivelson in their derivation of the effective quantum dimer model description of Heisenberg models to unprecedented accuracy for the spin-1/2 kagome, by including all the most important virtual singlet contributions on top of the orthogonalization of the nearest-neighbor valence bond singlet basis. Quite remarkably, the resulting picture is a competition between a Z2 spin liquid and a diamond valence bond crystal with a 12-site unit cell, as in the density-matrix renormalization group simulations of Yan et al. Furthermore, we found that, on cylinders of finite diameter d , there is a transition between the Z2 spin liquid at small d and the diamond valence bond crystal at large d , the prediction of the present microscopic description for the two-dimensional lattice. These results show that, if the ground state of the spin-1/2 kagome antiferromagnet can be described by nearest-neighbor singlet dimers, it is a diamond valence bond crystal, and, a contrario, that, if the system is a quantum spin liquid, it has to involve long-range singlets, consistent with the algebraic spin liquid scenario.

Pressure-induced valence and structure change in some anti-Th3P4 structure rare earth compounds

International Nuclear Information System (INIS)

Werner, A.; Hochheimer, H.D.; Jayaraman, A.; Bucher, E.

1981-01-01

The anti-Th 3 P 4 structure compounds Yb 4 Bi 3 and Yb 4 Sb 3 have been investigated to 350 kbar by high pressure X-ray diffraction, using the diamond anvil cell. From the P-V data it is found that Yb 4 Bi 3 and Yb 4 Sb 3 are much more compressible, compared to Sm 4 Bi 3 before the valence transition. This suggests that a continuous change in the valence state of Yb takes place with pressure in the two compounds and that they may be in the mixed valent state already at ambient pressure. The ''collapsed'' anti-Th 3 P 4 structure becomes unstable in Yb 4 Bi 3 and Yb 4 Sb 3 and new lines appear at high pressure, that fit the NaCl structure. The latter structure change seems to occur also in the electronically collapsed Sm 4 Bi 3 . The results are presented and discussed. (Auth.)

Valence band variation in Si (110) nanowire induced by a covered insulator

International Nuclear Information System (INIS)

Hong-Hua, Xu; Xiao-Yan, Liu; Yu-Hui, He; Gang, Du; Ru-Qi, Han; Jin-Feng, Kang; Chun, Fan; Ai-Dong, Sun

2010-01-01

In this work, we investigate strain effects induced by the deposition of gate dielectrics on the valence band structures in Si (110) nanowire via the simulation of strain distribution and the calculation of a generalized 6×6k·p strained valence band. The nanowire is surrounded by the gate dielectric. Our simulation indicates that the strain of the amorphous SiO 2 insulator is negligible without considering temperature factors. On the other hand, the thermal residual strain in a nanowire with amorphous SiO 2 insulator which has negligible lattice misfit strain pushes the valence subbands upwards by chemical vapour deposition and downwards by thermal oxidation treatment. In contrast with the strain of the amorphous SiO 2 insulator, the strain of the HfO 2 gate insulator in Si (110) nanowire pushes the valence subbands upwards remarkably. The thermal residual strain by HfO 2 insulator contributes to the up-shifting tendency. Our simulation results for valence band shifting and warping in Si nanowires can provide useful guidance for further nanowire device design. (classical areas of phenomenology)

Segregation of information about emotional arousal and valence in horse whinnies.

Science.gov (United States)

Briefer, Elodie F; Maigrot, Anne-Laure; Mandel, Roi; Freymond, Sabrina Briefer; Bachmann, Iris; Hillmann, Edna

2015-04-21

Studying vocal correlates of emotions is important to provide a better understanding of the evolution of emotion expression through cross-species comparisons. Emotions are composed of two main dimensions: emotional arousal (calm versus excited) and valence (negative versus positive). These two dimensions could be encoded in different vocal parameters (segregation of information) or in the same parameters, inducing a trade-off between cues indicating emotional arousal and valence. We investigated these two hypotheses in horses. We placed horses in five situations eliciting several arousal levels and positive as well as negative valence. Physiological and behavioral measures collected during the tests suggested the presence of different underlying emotions. First, using detailed vocal analyses, we discovered that all whinnies contained two fundamental frequencies ("F0" and "G0"), which were not harmonically related, suggesting biphonation. Second, we found that F0 and the energy spectrum encoded arousal, while G0 and whinny duration encoded valence. Our results show that cues to emotional arousal and valence are segregated in different, relatively independent parameters of horse whinnies. Most of the emotion-related changes to vocalizations that we observed are similar to those observed in humans and other species, suggesting that vocal expression of emotions has been conserved throughout evolution.

Valence-Specific Laterality Effects in Vocal Emotion: Interactions with Stimulus Type, Blocking and Sex

Science.gov (United States)

Schepman, Astrid; Rodway, Paul; Geddes, Pauline

2012-01-01

Valence-specific laterality effects have been frequently obtained in facial emotion perception but not in vocal emotion perception. We report a dichotic listening study further examining whether valence-specific laterality effects generalise to vocal emotions. Based on previous literature, we tested whether valence-specific laterality effects were…

Effect of the density of the electronic states at the valence orbital of the bridge redox molecule on the dependence of the tunnel current on the overvoltage in the case of fully adiabatic electron transition

International Nuclear Information System (INIS)

Medvedev, Igor G.

2008-01-01

Effect of the density of the electronic states at the valence orbital of the bridge redox molecule on the dependence of the tunnel current on the overvoltage and on the width at half maximum of the current-overvoltage curve is studied. A number of the approximate expressions for the density of states, the tunnel current and the width are obtained in the fully adiabatic limit for different particular cases. It is shown that at small values of the coupling of the electronic levels of the electrodes with the valence orbital of the redox molecule and the small values of the bias voltage two regions of the reorganization Gibbs energy exist with different dependence of the width on the reorganization Gibbs energy. The results of calculations of the density of states, the tunnel current and the width are presented and used for the interpretation of the experimental data [N.G. Tao, Phys. Rev. Lett. 76 (1996) 4066, I. Visoly-Fisher, K. Daie, Y. Terazono, C. Herrero, F. Fungo, L. Otero, E. Durantini, J.J. Silber, L. Sereno, D. Gust, T.A. Moore, A.L. Moore, S.M. Lindsay, PNAS 103 (2006) 8686

Early Events, Kinetic Intermediates and the Mechanism of Protein Folding in Cytochrome c

Directory of Open Access Journals (Sweden)

David S. Kliger

2009-04-01

Full Text Available Kinetic studies of the early events in cytochrome c folding are reviewed with a focus on the evidence for folding intermediates on the submillisecond timescale. Evidence from time-resolved absorption, circular dichroism, magnetic circular dichroism, fluorescence energy and electron transfer, small-angle X-ray scattering and amide hydrogen exchange studies on the t £ 1 ms timescale reveals a picture of cytochrome c folding that starts with the ~ 1-ms conformational diffusion dynamics of the unfolded chains. A fractional population of the unfolded chains collapses on the 1 – 100 ms timescale to a compact intermediate IC containing some native-like secondary structure. Although the existence and nature of IC as a discrete folding intermediate remains controversial, there is extensive high time-resolution kinetic evidence for the rapid formation of IC as a true intermediate, i.e., a metastable state separated from the unfolded state by a discrete free energy barrier. Final folding to the native state takes place on millisecond and longer timescales, depending on the presence of kinetic traps such as heme misligation and proline mis-isomerization. The high folding rates observed in equilibrium molten globule models suggest that IC may be a productive folding intermediate. Whether it is an obligatory step on the pathway to the high free energy barrier associated with millisecond timescale folding to the native state, however, remains to be determined.

The Hinge Segment of Human NADPH-Cytochrome P450 Reductase in Conformational Switching: The Critical Role of Ionic Strength

Directory of Open Access Journals (Sweden)

Diana Campelo

2017-10-01

Full Text Available NADPH-cytochrome P450 reductase (CPR is a redox partner of microsomal cytochromes P450 and is a prototype of the diflavin reductase family. CPR contains 3 distinct functional domains: a FMN-binding domain (acceptor reduction, a linker (hinge, and a connecting/FAD domain (NADPH oxidation. It has been demonstrated that the mechanism of CPR exhibits an important step in which it switches from a compact, closed conformation (locked state to an ensemble of open conformations (unlocked state, the latter enabling electron transfer to redox partners. The conformational equilibrium between the locked and unlocked states has been shown to be highly dependent on ionic strength, reinforcing the hypothesis of the presence of critical salt interactions at the interface between the FMN and connecting FAD domains. Here we show that specific residues of the hinge segment are important in the control of the conformational equilibrium of CPR. We constructed six single mutants and two double mutants of the human CPR, targeting residues G240, S243, I245 and R246 of the hinge segment, with the aim of modifying the flexibility or the potential ionic interactions of the hinge segment. We measured the reduction of cytochrome c at various salt concentrations of these 8 mutants, either in the soluble or membrane-bound form of human CPR. All mutants were found capable of reducing cytochrome c yet with different efficiency and their maximal rates of cytochrome c reduction were shifted to lower salt concentration. In particular, residue R246 seems to play a key role in a salt bridge network present at the interface of the hinge and the connecting domain. Interestingly, the effects of mutations, although similar, demonstrated specific differences when present in the soluble or membrane-bound context. Our results demonstrate that the electrostatic and flexibility properties of the hinge segment are critical for electron transfer from CPR to its redox partners.

New insight into the mechanism of mitochondrial cytochrome c function

DEFF Research Database (Denmark)

Chertkova, Rita V; Brazhe, Nadezda A; Bryantseva, Tatiana V

2017-01-01

We investigate functional role of the P76GTKMIFA83 fragment of the primary structure of cytochrome c. Based on the data obtained by the analysis of informational structure (ANIS), we propose a model of functioning of cytochrome c. According to this model, conformational rearrangements of the P76...... with conformational changes and reduced mobility of heme porphyrin. This points to a significant role of the P76GTKMIFA83 fragment in the electron transport function of cytochrome c....

Influence of polyhalogenated aromatic hydrocarbons on the induction, activity, and stabilization of cytochrome P450

International Nuclear Information System (INIS)

Voorman, R.

1987-01-01

In the course of experiments evaluating the metabolism of polybrominated biphenyls by cytochrome P450 isozymes induced by 3,4,5,3',4',5'-hexabromobiphenyl (HBB), it was discovered that the inducer remained closely associated with cytochrome P450d. Subsequent purification of cytochromes from HBB treated rates revealed a 0.5:1 association of HBB to cytochrome P450d but virtually none with cytochrome P450c or cytochrome b5. Immunochemical quantitation of cytochrome P450d in the same microsomes yielded a ratio of P450d:HBB that approached unity. Measurement of cytochrome P450d estradiol 2-hydroxylase indicated non-competitive or mixed type inhibition caused by HBB at a concentration of 10-1000 nM. Inhibition was specific to cytochrome P450d since estradiol 2-hydroxylase catalyzed by cytochrome P450h was unaffected by HBB. The ability of HCB and isosafrole to stabilize cytochrome P450d, and thus indirectly influence regulation of the enzyme, was evaluated by treating rats with a dose of TCDD sufficient to produce maximum induction of cytochromes P450c and P450d via the Ah receptor, yet insufficient to bind to the enzyme. Subsequent treatment of these animals with HCB or isosafrole and a radiolabeled amino acid, revealed a significant increase in cytochrome P450d specific content relative to cytochrome P450c and significant retention of the radiolabel in P450d relative to rats treated only with TCDD

Modulation of motor-meaning congruity effects for valenced words

OpenAIRE

Brookshire, Geoffrey; Ivry, Richard; Casasanto, Daniel

2010-01-01

We investigated the extent to which emotionally valenced words automatically cue spatio-motor representations. Participants made speeded button presses, moving their hand upward or downward while viewing words with positive or negative valence. Only the color of the words was relevant to the response; on target trials, there was no requirement to read the words or process their meaning. In Experiment 1, upward responses were faster for positive words, and downward for negative words. This eff...

Influence of emotional valence and arousal on the spread of activation in memory.

Science.gov (United States)

Jhean-Larose, Sandra; Leveau, Nicolas; Denhière, Guy

2014-11-01

Controversy still persists on whether emotional valence and arousal influence cognitive activities. Our study sought to compare how these two factors foster the spread of activation within the semantic network. In a lexical decision task, prime words were varied depending on the valence (pleasant or unpleasant) or on the level of emotional arousal (high or low). Target words were carefully selected to avoid semantic priming effects, as well as to avoid arousing specific emotions (neutral). Three SOA durations (220, 420 and 720 ms) were applied across three independent groups. Results indicate that at 220 ms, the effect of arousal is significantly higher than the effect of valence in facilitating spreading activation while at 420 ms, the effect of valence is significantly higher than the effect of arousal in facilitating spreading activation. These findings suggest that affect is a sequential process involving the successive intervention of arousal and valence.

16O + 16O + valence neutrons in molecular orbitals structures of positive- and negative-parity superdeformed bands in 34S

International Nuclear Information System (INIS)

Taniguchi, Yasutaka

2015-01-01

The structures of superdeformed (SD) states in 34 S have been investigated using the antisymmetrized molecular dynamics and generator coordinate method (GCM). The GCM basis wave functions are calculated via energy variation with a constraint on the quadrupole deformation parameter β. By applying the GCM after parity and angular momentum projections, the coexistence of two positive- and one negative-parity SD bands are predicted, and low-lying states and other deformed bands are obtained. The SD bands have structures of 16 O + 16 O + two valence neutrons in molecular orbitals around the two 16 O cores in a cluster picture. The configurations of the two valence neutrons are δ 2 and π 2 for the positive-parity SD bands and π 1 δ 1 for the negative-parity SD band. (author)

16O + 16O + valence neutrons in molecular orbitals structures of positive- and negative-parity superdeformed bands in 34S

International Nuclear Information System (INIS)

Taniguchi, Yasutaka

2014-01-01

The structures of superdeformed (SD) states in 34 S are investigated using the antisymmetrized molecular dynamics and generator coordinate method (GCM). The GCM basis wave functions are calculated via energy variation with a constraint on the quadrupole deformation parameter β. By applying the GCM after parity and angular momentum projections, the coexistence of two positive- and one negative-parity SD bands are predicted, and low-lying states and other deformed bands are obtained. The SD bands have structures of 16 O + 16 O + two valence neutrons in molecular orbitals around the two 16 O cores in a cluster picture. The configurations of the two valence neutrons are δ 2 and π 2 for the positive-parity SD bands and π 1 δ 1 for the negative-parity SD band

Purification and characterization of NADPH--cytochrome c reductase from the midgut of the southern armyworm (Spodoptera eridania).

Science.gov (United States)

Crankshaw, D L; Hetnarski, K; Wilkinson, C F

1979-09-01

1. NADPH-cytochrome c reductase was solubilized with bromelain and purified about 400-fold from sucrose/pyrophosphate-washed microsomal fractions from southern armyworm (Spodoptera eridania) larval midguts. 2. The enzyme has a mol.wt. of 70 035 +/- 1300 and contained 2 mol of flavin/mol of enzyme consisting of almost equimolar amounts of FMN and FAD. 3. Aerobic titration of the enzyme with NADPH caused the formation of a stable half-reduced state at 0.5 mol of NADPH/mol of flavin. 4. Kinetic analysis showed that the reduction of cytochrome c proceeded by a Bi Bi Ping Pong mechanism. 5. Apparent Km values for NADPH and cytochrome c and Ki values for NADP+ and 2'-AMP were considerably higher for the insect reductase than for the mammalian liver enzyme. 6. These are discussed in relation to possible differences in the active sites of the enzymes.

Valence band structure and density of states effective mass model of biaxial tensile strained silicon based on k · p theory

International Nuclear Information System (INIS)

Kuang Qian-Wei; Liu Hong-Xia; Wang Shu-Long; Qin Shan-Shan; Wang Zhi-Lin

2011-01-01

After constructing a stress and strain model, the valence bands of in-plane biaxial tensile strained Si is calculated by k · p method. In the paper we calculate the accurate anisotropy valance bands and the splitting energy between light and heavy hole bands. The results show that the valance bands are highly distorted, and the anisotropy is more obvious. To obtain the density of states (DOS) effective mass, which is a very important parameter for device modeling, a DOS effective mass model of biaxial tensile strained Si is constructed based on the valance band calculation. This model can be directly used in the device model of metal—oxide semiconductor field effect transistor (MOSFET). It also a provides valuable reference for biaxial tensile strained silicon MOSFET design. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

Immunohistochemical detection of cytochrome P450 isoenzymes in cultured human epidermal cells.

Science.gov (United States)

Van Pelt, F N; Meierink, Y J; Blaauboer, B J; Weterings, P J

1990-12-01

We used specific monoclonal antibodies (MAb) to human cytochrome P450 isoenzymes to determine the presence of these proteins in human epidermal cells. Two MAb (P450-5 and P450-8) recognize major forms of hepatic cytochrome P450 involved in biotransformation of xenobiotics. A third MAb, to cytochrome P450-9, is not fully characterized. The proteins were determined by the indirect immunoperoxidase technique after fixation with methanol and acetone. Biopsy materials for cultured keratinocytes, i.e., foreskin and hair follicles, contained the two major forms of cytochrome P450. In cultured keratinocytes derived from hair follicles the proteins were undetectable, whereas the keratinocytes derived from foreskin continued to express the two major forms of hepatic cytochrome P450. Cultured human fibroblasts and a human keratinocyte cell line (SVK14) showed staining similar to that of the foreskin keratinocytes. Cytochrome P450-9 was detectable only in human hepatocytes. The results indicate that, under the culture conditions applied, cultured human foreskin cells and the cell line SVK14 continue to express specific cytochrome P450 isoenzymes in culture, in contrast to hair follicle keratinocytes.

Age-related emotional bias in processing two emotionally valenced tasks.

Science.gov (United States)

Allen, Philip A; Lien, Mei-Ching; Jardin, Elliott

2017-01-01

Previous studies suggest that older adults process positive emotions more efficiently than negative emotions, whereas younger adults show the reverse effect. We examined whether this age-related difference in emotional bias still occurs when attention is engaged in two emotional tasks. We used a psychological refractory period paradigm and varied the emotional valence of Task 1 and Task 2. In both experiments, Task 1 was emotional face discrimination (happy vs. angry faces) and Task 2 was sound discrimination (laugh, punch, vs. cork pop in Experiment 1 and laugh vs. scream in Experiment 2). The backward emotional correspondence effect for positively and negatively valenced Task 2 on Task 1 was measured. In both experiments, younger adults showed a backward correspondence effect from a negatively valenced Task 2, suggesting parallel processing of negatively valenced stimuli. Older adults showed similar negativity bias in Experiment 2 with a more salient negative sound ("scream" relative to "punch"). These results are consistent with an arousal-bias competition model [Mather and Sutherland (Perspectives in Psychological Sciences 6:114-133, 2011)], suggesting that emotional arousal modulates top-down attentional control settings (emotional regulation) with age.

Cloning, DNA sequence, and expression of the Rhodobacter sphaeroides cytochrome c/sub 2/ gene

Energy Technology Data Exchange (ETDEWEB)

Donohue, T.J.; McEwan, A.G.; Kaplan, S.

1986-11-01

The Rhodobacter sphaeroides cytochrome c/sub 2/ functions as a mobile electron carrier in both aerobic and photosynthetic electron transport chains. Synthetic deoxyoligonucleotide probes, based on the known amino acid sequence of this protein (M/sub r/ 14,000), were used to identify and clone the cytochrome c/sub 2/ structural gene (cycA). DNA sequence analysis of the cycA gene indicated the presence of a typical procaryotic 21-residue signal sequence, suggesting that this periplasmic protein is synthesized in vivo as a precursor. Synthesis of an immunoreactive cytochrome c/sub 2/ precursor protein (M/sub r/ 15,500) was observed in vitro when plasmids containing the cycA gene were used as templates in an R. sphaeroides coupled transcription-translation system. Approximately 500 base pairs of DNA upstream of the cycA gene was sufficient to allow expression of this gene product in vitro. Northern blot analysis with an internal cycA-specific probe identified at least two possibly monocistronic transcripts present in both different cellular levels and relative stoichiometries in steady-state cells grown under different physiological conditions. The ratio of the small (740-mucleotide) and large (920-nucleotide) cycA-specific mRNA species was dependent on cultural conditions but was not affected by light intensity under photosynthetic conditions. These results suggest that the increase in the cellular level of the cytochrome c/sub 2/ protein found in photosynthetic cells was due, in part, to increased transcription of the single-copy cyc operon.

Photoion mass spectroscopy and valence photoionization of hypoxanthine, xanthine and caffeine

Energy Technology Data Exchange (ETDEWEB)

Feyer, Vitaliy, E-mail: vitaliy.feyer@elettra.trieste.it [Sincrotrone Trieste, in Area Science Park, I-34012 Basovizza (Trieste) (Italy); Plekan, Oksana [Sincrotrone Trieste, in Area Science Park, I-34012 Basovizza (Trieste) (Italy)] [Institute of Electron Physics, 21 Universitetska St., 88017 Uzhgorod (Ukraine); Richter, Robert [Sincrotrone Trieste, in Area Science Park, I-34012 Basovizza (Trieste) (Italy); Coreno, Marcello [CNR-IMIP, Area della Ricerca di Roma 1, CP10, I-00016 Monterotondo Scalo (Italy)] [CNR-Laboratorio Nazionale TASC-INFM, I-34012 Basovizza (Trieste) (Italy); Prince, Kevin C. [Sincrotrone Trieste, in Area Science Park, I-34012 Basovizza (Trieste) (Italy)] [CNR-Laboratorio Nazionale TASC-INFM, I-34012 Basovizza (Trieste) (Italy)

2009-03-30

Photoionization mass spectra of hypoxanthine, xanthine and caffeine were measured using the photoelectron-photoion coincidence technique and noble gas resonance radiation at energies from 8.4 to 21.2 eV for ionization. The fragmentation patterns for these compounds show that hydrogen cyanide is the main neutral loss species at higher photon energies, while photoionization below 16.67 eV led predominantly to the parent ion. The valence photoelectron spectra of this family of molecules were measured over an extended energy range, including the inner C, N and O 2s valence orbitals. The observed ion fragments were related to ionization of the valence orbitals.

Mitochondrial cytochrome c biogenesis: no longer an enigma.

Science.gov (United States)

Babbitt, Shalon E; Sutherland, Molly C; San Francisco, Brian; Mendez, Deanna L; Kranz, Robert G

2015-08-01

Cytochromes c (cyt c) and c1 are heme proteins that are essential for aerobic respiration. Release of cyt c from mitochondria is an important signal in apoptosis initiation. Biogenesis of c-type cytochromes involves covalent attachment of heme to two cysteines (at a conserved CXXCH sequence) in the apocytochrome. Heme attachment is catalyzed in most mitochondria by holocytochrome c synthase (HCCS), which is also necessary for the import of apocytochrome c (apocyt c). Thus, HCCS affects cellular levels of cyt c, impacting mitochondrial physiology and cell death. Here, we review the mechanisms of HCCS function and the roles of heme and residues in the CXXCH motif. Additionally, we consider concepts emerging within the two prokaryotic cytochrome c biogenesis pathways. Copyright © 2015 Elsevier Ltd. All rights reserved.

Cytochromes c': Structure, Reactivity and Relevance to Haem-Based Gas Sensing.

Science.gov (United States)

Hough, Michael A; Andrew, Colin R

2015-01-01

Cytochromes c' are a group of class IIa cytochromes with pentacoordinate haem centres and are found in photosynthetic, denitrifying and methanotrophic bacteria. Their function remains unclear, although roles in nitric oxide (NO) trafficking during denitrification or in cellular defence against nitrosoative stress have been proposed. Cytochromes c' are typically dimeric with each c-type haem-containing monomer folding as a four-α-helix bundle. Their hydrophobic and crowded distal sites impose severe restrictions on the binding of distal ligands, including diatomic gases. By contrast, NO binds to the proximal haem face in a similar manner to that of the eukaryotic NO sensor, soluble guanylate cyclase and bacterial analogues. In this review, we focus on how structural features of cytochromes c' influence haem spectroscopy and reactivity with NO, CO and O2. We also discuss the relevance of cytochrome c' to understanding the mechanisms of gas binding to haem-based sensor proteins. © 2015 Elsevier Ltd. All rights reserved.

A cytosolic cytochrome b 5-like protein in yeast cell accelerating the electron transfer from NADPH to cytochrome c catalyzed by Old Yellow Enzyme

International Nuclear Information System (INIS)

Nakagawa, Manabu; Yamano, Toshio; Kuroda, Kiyo; Nonaka, Yasuki; Tojo, Hiromasa; Fujii, Shigeru

2005-01-01

A 410-nm absorbing species which enhanced the reduction rate of cytochrome c by Old Yellow Enzyme (OYE) with NADPH was found in Saccharomyces cerevisiae. It was solubilized together with OYE by the treatment of yeast cells with 10% ethyl acetate. The purified species showed visible absorption spectra in both oxidized and reduced forms, which were the same as those of the yeast microsomal cytochrome b 5 . At least 14 amino acid residues of the N-terminal region coincided with those of yeast microsomal b 5 , but the protein had a lower molecular weight determined to be 12,600 by SDS-PAGE and 9775 by mass spectrometry. The cytochrome b 5 -like protein enhanced the reduction rate of cytochrome c by OYE, and a plot of the reduction rates against its concentration showed a sigmoidal curve with an inflexion point at 6 x 10 -8 M of the protein

Redox active molecules cytochrome c and vitamin C enhance heme-enzyme peroxidations by serving as non-specific agents for redox relay

Energy Technology Data Exchange (ETDEWEB)

Gade, Sudeep Kumar; Bhattacharya, Subarna [Heme and Flavo Proteins Laboratory, 204, Center for Biomedical Research, VIT University, Vellore, Tamil Nadu 632014 (India); Manoj, Kelath Murali, E-mail: satyamjayatu@yahoo.com [Heme and Flavo Proteins Laboratory, 204, Center for Biomedical Research, VIT University, Vellore, Tamil Nadu 632014 (India)

2012-03-09

Highlights: Black-Right-Pointing-Pointer At low concentrations, cytochrome c/vitamin C do not catalyze peroxidations. Black-Right-Pointing-Pointer But low levels of cytochrome c/vitamin C enhance diverse heme peroxidase activities. Black-Right-Pointing-Pointer Enhancement positively correlates to the concentration of peroxide in reaction. Black-Right-Pointing-Pointer Reducible additives serve as non-specific agents for redox relay in the system. Black-Right-Pointing-Pointer Insight into electron transfer processes in routine and oxidative-stress states. -- Abstract: We report that incorporation of very low concentrations of redox protein cytochrome c and redox active small molecule vitamin C impacted the outcome of one-electron oxidations mediated by structurally distinct plant/fungal heme peroxidases. Evidence suggests that cytochrome c and vitamin C function as a redox relay for diffusible reduced oxygen species in the reaction system, without invoking specific or affinity-based molecular interactions for electron transfers. The findings provide novel perspectives to understanding - (1) the promiscuous role of cytochrome b{sub 5} in the metabolism mediated by liver microsomal xenobiotic metabolizing systems and (2) the roles of antioxidant molecules in affording relief from oxidative stress.

Clustering of low-valence particles: structure and kinetics.

Science.gov (United States)

Markova, Olga; Alberts, Jonathan; Munro, Edwin; Lenne, Pierre-François

2014-08-01

We compute the structure and kinetics of two systems of low-valence particles with three or six freely oriented bonds in two dimensions. The structure of clusters formed by trivalent particles is complex with loops and holes, while hexavalent particles self-organize into regular and compact structures. We identify the elementary structures which compose the clusters of trivalent particles. At initial stages of clustering, the clusters of trivalent particles grow with a power-law time dependence. Yet at longer times fusion and fission of clusters equilibrates and clusters form a heterogeneous phase with polydispersed sizes. These results emphasize the role of valence in the kinetics and stability of finite-size clusters.

c-Type cytochrome-dependent formation of U(IV nanoparticles by Shewanella oneidensis.

Directory of Open Access Journals (Sweden)

Matthew J Marshall

2006-09-01

Full Text Available Modern approaches for bioremediation of radionuclide contaminated environments are based on the ability of microorganisms to effectively catalyze changes in the oxidation states of metals that in turn influence their solubility. Although microbial metal reduction has been identified as an effective means for immobilizing highly-soluble uranium(VI complexes in situ, the biomolecular mechanisms of U(VI reduction are not well understood. Here, we show that c-type cytochromes of a dissimilatory metal-reducing bacterium, Shewanella oneidensis MR-1, are essential for the reduction of U(VI and formation of extracellular UO(2 nanoparticles. In particular, the outer membrane (OM decaheme cytochrome MtrC (metal reduction, previously implicated in Mn(IV and Fe(III reduction, directly transferred electrons to U(VI. Additionally, deletions of mtrC and/or omcA significantly affected the in vivo U(VI reduction rate relative to wild-type MR-1. Similar to the wild-type, the mutants accumulated UO(2 nanoparticles extracellularly to high densities in association with an extracellular polymeric substance (EPS. In wild-type cells, this UO(2-EPS matrix exhibited glycocalyx-like properties and contained multiple elements of the OM, polysaccharide, and heme-containing proteins. Using a novel combination of methods including synchrotron-based X-ray fluorescence microscopy and high-resolution immune-electron microscopy, we demonstrate a close association of the extracellular UO(2 nanoparticles with MtrC and OmcA (outer membrane cytochrome. This is the first study to our knowledge to directly localize the OM-associated cytochromes with EPS, which contains biogenic UO(2 nanoparticles. In the environment, such association of UO(2 nanoparticles with biopolymers may exert a strong influence on subsequent behavior including susceptibility to oxidation by O(2 or transport in soils and sediments.

Intestinal cytochromes P450 regulating the intestinal microbiota and its probiotic profile

Directory of Open Access Journals (Sweden)

Eugenia Elefterios Venizelos Bezirtzoglou

2012-09-01

Full Text Available Cytochromes P450 (CYPs enzymes metabolize a large variety of xenobiotic substances. In this vein, a plethora of studies were conducted to investigate their role, as cytochromes are located in both liver and intestinal tissues. The P450 profile of the human intestine has not been fully characterized. Human intestine serves primarily as an absorptive organ for nutrients, although it has also the ability to metabolize drugs. CYPs are responsible for the majority of phase I drug metabolism reactions. CYP3A represents the major intestinal CYP (80% followed by CYP2C9. CYP1A is expressed at high level in the duodenum, together with less abundant levels of CYP2C8-10 and CYP2D6. Cytochromes present a genetic polymorphism intra- or interindividual and intra- or interethnic. Changes in the pharmacokinetic profile of the drug are associated with increased toxicity due to reduced metabolism, altered efficacy of the drug, increased production of toxic metabolites, and adverse drug interaction. The high metabolic capacity of the intestinal flora is due to its enormous pool of enzymes, which catalyzes reactions in phase I and phase II drug metabolism. Compromised intestinal barrier conditions, when rupture of the intestinal integrity occurs, could increase passive paracellular absorption. It is clear that high microbial intestinal charge following intestinal disturbances, ageing, environment, or food-associated ailments leads to the microbial metabolism of a drug before absorption. The effect of certain bacteria having a benefic action on the intestinal ecosystem has been largely discussed during the past few years by many authors. The aim of the probiotic approach is to repair the deficiencies in the gut flora and establish a protective effect. There is a tentative multifactorial association of the CYP (P450 cytochrome role in the different diseases states, environmental toxic effects or chemical exposures and nutritional status.

Transfer of chirality from adsorbed chiral molecules to the substrates highlighted by circular dichroism in angle-resolved valence photoelectron spectroscopy

DEFF Research Database (Denmark)

Contini, G.; Turchini, S.; Sanna, Simone

2012-01-01

Studies of self-assembled chiral molecules on achiral metallic surfaces have mostly focused on the determination of the geometry of adsorbates and their electronic structure. The aim of this paper is to provide direct information on the chirality character of the system and on the chirality...... transfer from molecules to substrate by means of circular dichroism in the angular distribution of valence photoelectrons for the extended domain of the chiral self-assembled molecular structure, formed by alaninol adsorbed on Cu(100). We show, by the dichroic behavior of a mixed molecule–copper valence...... state, that the presence of molecular chiral domains induces asymmetry in the interaction with the substrate and locally transfers the chiral character to the underlying metal atoms participating in the adsorption process; combined information related to the asymmetry of the initial electronic state...

The novel cytochrome c6 of chloroplasts: a case of evolutionary bricolage?

Science.gov (United States)

Howe, Christopher J; Schlarb-Ridley, Beatrix G; Wastl, Juergen; Purton, Saul; Bendall, Derek S

2006-01-01

Cytochrome c6 has long been known as a redox carrier of the thylakoid lumen of cyanobacteria and some eukaryotic algae that can substitute for plastocyanin in electron transfer. Until recently, it was widely accepted that land plants lack a cytochrome c6. However, a homologue of the protein has now been identified in several plant species together with an additional isoform in the green alga Chlamydomonas reinhardtii. This form of the protein, designated cytochrome c6A, differs from the 'conventional' cytochrome c6 in possessing a conserved insertion of 12 amino acids that includes two absolutely conserved cysteine residues. There are conflicting reports of whether cytochrome c6A can substitute for plastocyanin in photosynthetic electron transfer. The evidence for and against this is reviewed and the likely evolutionary history of cytochrome c6A is discussed. It is suggested that it has been converted from a primary role in electron transfer to one in regulation within the chloroplast, and is an example of evolutionary 'bricolage'.

Active site intermediates in the reduction of O(2) by cytochrome oxidase, and their derivatives.

Science.gov (United States)

Wikström, Mårten

2012-04-01

The mechanism of dioxygen activation and reduction in cell respiration, as catalysed by cytochrome c oxidase, has a long history. The work by Otto Warburg, David Keilin and Britton Chance defined the dioxygen-binding heme iron centre, viz. das Atmungsferment, or cytochrome a(3). Chance brought the field further in the mid-1970's by ingenious low-temperature studies that for the first time identified the primary enzyme-substrate (ES) Michaelis complex of cell respiration, the dioxygen adduct of heme a(3), which he termed Compound A. Further work using optical, resonance Raman, EPR, and other sophisticated spectroscopic techniques, some of which with microsecond time resolution, has brought us to the situation today, where major principles of how O(2) reduction occurs in respiration are well understood. Nonetheless, some questions have remained open, for example concerning the precise structures, catalytic roles, and spectroscopic properties of the breakdown products of Compound A that have been called P, F (for peroxy and ferryl), and O (oxidised). This nomenclature has been known to be inadequate for some time already, and an alternative will be suggested here. In addition, the multiple forms of P, F and O states have been confusing, a situation that we endeavour to help clarifying. The P and F states formed artificially by reacting cytochrome oxidase with hydrogen peroxide are especially scrutinised, and some novel interpretations will be given that may account for previously unexplained observations. Copyright © 2011 Elsevier B.V. All rights reserved.

The bidirectional congruency effect of brightness-valence metaphoric association in the Stroop-like and priming paradigms.

Science.gov (United States)

Huang, Yanli; Tse, Chi-Shing; Xie, Jiushu

2017-11-04

The conceptual metaphor theory (Lakoff & Johnson, 1980, 1999) postulates a unidirectional metaphoric association between abstract and concrete concepts: sensorimotor experience activated by concrete concepts facilitates the processing of abstract concepts, but not the other way around. However, this unidirectional view has been challenged by studies that reported a bidirectional metaphoric association. In three experiments, we tested the directionality of the brightness-valence metaphoric association, using Stroop-like paradigm, priming paradigm, and Stroop-like paradigm with a go/no-go manipulation. Both mean and vincentile analyses of reaction time data were performed. We showed that the directionality of brightness-valence metaphoric congruency effect could be modulated by the activation level of the brightness/valence information. Both brightness-to-valence and valence-to-brightness metaphoric congruency effects occurred in the priming paradigm, which could be attributed to the presentation of prime that pre-activated the brightness or valence information. However, in the Stroop-like paradigm the metaphoric congruency effect was only observed in the brightness-to-valence direction, but not in the valence-to-brightness direction. When the go/no-go manipulation was used to boost the activation of word meaning in the Stroop-like paradigm, the valence-to-brightness metaphoric congruency effect was observed. Vincentile analyses further revealed that valence-to-brightness metaphoric congruency effect approached significance in the Stroop-like paradigm when participants' reaction times were slower (at around 490ms). The implications of the current findings on the conceptual metaphor theory and embodied cognition are discussed. Copyright © 2017 Elsevier B.V. All rights reserved.

Graduate radiographers' expectations for role development - The potential impact of misalignment of expectation and valence on staff retention and service provision

International Nuclear Information System (INIS)

Williamson, Keren; Mundy, Lynn A.

2010-01-01

Purpose: The purpose of this study was to investigate the role development expectations of graduate radiographers with a view to predicting the potential impact of a misalignment of these expectations and valence on service delivery and staff retention. A final year cohort of radiography students completed a questionnaire designed to explore topics associated with role development opportunities. Method: Structured questionnaires, in the Likert scale format, utilised 20 attitude questions constructed to elicit information in relation to 3 main themes of investigation; expectation, valence and knowledge. Results: All participants (n = 37) stated an expectation for role development opportunities with 97.3% (n = 36) indicating that these expectations would be realised within 5 years of graduation and 75.7% (n = 28) within 2 years of graduation. A significant correlation between expectation for role development and job satisfaction was seen (p < 0.05). 81.1% (n = 30) of participants stated turnover intentions in order to meet their expectations. Conclusion: There is an expectation for role development opportunities for new graduates with a valence noted of the intrinsic reward of meeting these expectations. Expectation and valence are seen to be intrinsically linked with job satisfaction suggesting that misalignment of these would have a potentially negative impact on motivation and retention of the future radiography workforce demonstrating a positive correlation with withdrawal behaviours, including turnover intentions. In a relatively small professional group such as radiography the phenomenon of group cohesion may be strong suggesting that withdrawal behaviours may manifest as 'resignation in post', impacting on the quality of care and service provision for patients.

Cerium valence change in the solid solutions Ce(Rh1-xRux)Sn

International Nuclear Information System (INIS)

Niehaus, Oliver; Riecken, Jan F.; Winter, Florian; Poettgen, Rainer; Muenster Univ.; Abdala, Paula M.; Chevalier, Bernard

2013-01-01

The solid solutions Ce(Rh 1-x Ru x )Sn were investigated by means of susceptibility measurements, specific heat, electrical resistivity, X-ray absorption spectroscopy (XAS), and 119 Sn Moessbauer spectroscopy. Magnetic measurements as well as XAS data show a cerium valence change in dependence on the ruthenium content. Higher ruthenium content causes an increase from 3.22 to 3.45 at 300 K. Furthermore χ and χ -1 data indicate valence fluctuation for cerium as a function of temperature. For example, Ce(Rh 0.8 Ru 0.2 )Sn exhibits valence fluctuations between 3.42 and 3.32 in the temperature range of 10 to 300 K. This could be proven by using the interconfiguration fluctuation (ICF) model introduced by Sales and Wohlleben. Cerium valence change does not influence the tin atoms as proven by 119 Sn Moessbauer spectroscopy, but it influences the electrical properties. Ce(Rh 0.9 Ru 0.1 )Sn behaves like a typical valence fluctuating compound, and higher ruthenium content causes an increase of the metallic behavior. (orig.)

Valency stabilization of Polyvalent Iron Ions in Solution By some Organic additives during Gamma Irradiation

International Nuclear Information System (INIS)

Barakat, M.F.; Abdel Hamid, M.M.

2012-01-01

Valency stabilization of polyvalent ions in gamma irradiated aqueous solutions is sometimes necessary for the success of some chemical operations. In some previous publications valency stabilization of some polyvalent ions in solution upon gamma irradiation was achieved by using additives capable of interacting with the oxidizing or reducing species formed by water radiolysis in the medium. The results showed that the duration of valency stabilization depends on the concentration of the additives used.In the present work, a series of some organic additives has been used to investigate their capability in inducing valency stabilization of polyvalent iron ions when subjected to extended gamma irradiation periods. The results showed that the efficiency of valency stabilization depends on the amount and chemical structure of the organic additive used

Investigation of the redox-dependent modulation of structure and dynamics in human cytochrome c

Energy Technology Data Exchange (ETDEWEB)

Imai, Mizue [Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo 060-0810 (Japan); Saio, Tomohide [Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo 060-0810 (Japan); Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060-0810 (Japan); Kumeta, Hiroyuki [Faculty of Advanced Life Science, Hokkaido University, Sapporo 001-0021 (Japan); Uchida, Takeshi [Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo 060-0810 (Japan); Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060-0810 (Japan); Inagaki, Fuyuhiko [Faculty of Advanced Life Science, Hokkaido University, Sapporo 001-0021 (Japan); Ishimori, Koichiro, E-mail: koichiro@sci.hokudai.ac.jp [Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo 060-0810 (Japan); Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060-0810 (Japan)

2016-01-22

Redox-dependent changes in the structure and dynamics of human cytochrome c (Cyt c) were investigated by solution NMR. We found significant structural changes in several regions, including residues 23–28 (loop 3), which were further corroborated by chemical shift differences between the reduced and oxidized states of Cyt c. These differences are essential for discriminating redox states in Cyt c by cytochrome c oxidase (CcO) during electron transfer reactions. Carr-Purcell-Meiboom-Gill (CPMG) relaxation dispersion experiments identified that the region around His33 undergoes conformational exchanges on the μs-ms timescale, indicating significant redox-dependent structural changes. Because His33 is not part of the interaction site for CcO, our data suggest that the dynamic properties of the region, which is far from the interaction site for CcO, contribute to conformational changes during electron transfer to CcO. - Highlights: • Solution structure and dynamics analysis for human Cyt c by NMR. • Structural changes responsible for the discrimination of the redox state in Cyt c. • Conformational exchange in the region outside of the interaction site for CcO. • Less flexibility and rigid structure of the interaction site on Cyt c for CcO.

Approach and withdrawal tendencies during written word processing: effects of task, emotional valence and emotional arousal

OpenAIRE

Citron, Francesca Maria Marina; Abugaber, David; Herbert, Cornelia

2016-01-01

The affective dimensions of emotional valence and emotional arousal affect processing of verbal and pictorial stimuli. Traditional emotional theories assume a linear relationship between these dimensions, with valence determining the direction of a behaviour (approach vs. withdrawal) and arousal its intensity or strength. In contrast, according to the valence-arousal conflict theory, both dimensions are interactively related: positive valence and low arousal (PL) are associated with an implic...

The power of emotional valence – From cognitive to affective processes in reading

OpenAIRE

Ulrike eAltmann; Ulrike eAltmann; Isabel C Bohrn; Isabel C Bohrn; Oliver eLubrich; Oliver eLubrich; Winfried eMenninghaus; Winfried eMenninghaus; Arthur M Jacobs; Arthur M Jacobs; Arthur M Jacobs

2012-01-01

The comprehension of stories requires the reader to imagine the cognitive and affective states of the characters. The content of many stories is unpleasant, as they often deal with conflict, disturbance or crisis. Nevertheless, unpleasant stories can be liked and enjoyed. In this fMRI study, we used a parametric approach to examine (1) the capacity of increasing negative valence of story contents to activate the mentalizing network (cognitive and affective theory of mind, ToM), and (2) the ne...

Importance of c-Type cytochromes for U(VI reduction by Geobacter sulfurreducens

Directory of Open Access Journals (Sweden)

Leang Ching

2007-03-01

Full Text Available Abstract Background In order to study the mechanism of U(VI reduction, the effect of deleting c-type cytochrome genes on the capacity of Geobacter sulfurreducens to reduce U(VI with acetate serving as the electron donor was investigated. Results The ability of several c-type cytochrome deficient mutants to reduce U(VI was lower than that of the wild type strain. Elimination of two confirmed outer membrane cytochromes and two putative outer membrane cytochromes significantly decreased (ca. 50–60% the ability of G. sulfurreducens to reduce U(VI. Involvement in U(VI reduction did not appear to be a general property of outer membrane cytochromes, as elimination of two other confirmed outer membrane cytochromes, OmcB and OmcC, had very little impact on U(VI reduction. Among the periplasmic cytochromes, only MacA, proposed to transfer electrons from the inner membrane to the periplasm, appeared to play a significant role in U(VI reduction. A subpopulation of both wild type and U(VI reduction-impaired cells, 24–30%, accumulated amorphous uranium in the periplasm. Comparison of uranium-accumulating cells demonstrated a similar amount of periplasmic uranium accumulation in U(VI reduction-impaired and wild type G. sulfurreducens. Assessment of the ability of the various suspensions to reduce Fe(III revealed no correlation between the impact of cytochrome deletion on U(VI reduction and reduction of Fe(III hydroxide and chelated Fe(III. Conclusion This study indicates that c-type cytochromes are involved in U(VI reduction by Geobacter sulfurreducens. The data provide new evidence for extracellular uranium reduction by G. sulfurreducens but do not rule out the possibility of periplasmic uranium reduction. Occurrence of U(VI reduction at the cell surface is supported by the significant impact of elimination of outer membrane cytochromes on U(VI reduction and the lack of correlation between periplasmic uranium accumulation and the capacity for uranium

Changing the conversation: the influence of emotions on conversational valence and alcohol consumption.

Science.gov (United States)

Hendriks, Hanneke; van den Putte, Bas; de Bruijn, Gert-Jan

2014-10-01

Health campaign effects may be improved by taking interpersonal communication processes into account. The current study, which employed an experimental, pretest-posttest, randomized exposure design (N = 208), investigated whether the emotions induced by anti-alcohol messages influence conversational valence about alcohol and subsequent persuasion outcomes. The study produced three main findings. First, an increase in the emotion fear induced a negative conversational valence about alcohol. Second, fear was most strongly induced by a disgusting message, whereas a humorous appeal induced the least fear. Third, a negative conversational valence elicited healthier binge drinking attitudes, subjective norms, perceived behavioral control, intentions, and behaviors. Thus, health campaign planners and health researchers should pay special attention to the emotional characteristics of health messages and should focus on inducing a healthy conversational valence.

Nitrate as a probe of cytochrome c surface: crystallographic identification of crucial "hot spots" for protein-protein recognition.

Science.gov (United States)

De March, Matteo; Demitri, Nicola; De Zorzi, Rita; Casini, Angela; Gabbiani, Chiara; Guerri, Annalisa; Messori, Luigi; Geremia, Silvano

2014-06-01

The electrostatic surface of cytochrome c and its changes with the iron oxidation state are involved in the docking and undocking processes of this protein to its biological partners in the mitochondrial respiratory pathway. To investigate the subtle mechanisms of formation of productive macromolecular complexes and of their breakage following the electron transfer process, the X-ray structures of horse heart ferri-cytochrome c (trigonal form) and ferro-cytochrome c (monoclinic form) were obtained using nitrate ions both as a crystallizing agent and an anionic probe for mapping the electrostatic surface changes. Both crystal forms contain three protein molecules in the asymmetric unit. In addition, a total of 21.5 and 18 crystallographically independent nitrate ions were identified for the trigonal and monoclinic forms, respectively. By matching all the six crystallographically independent protein molecules, 26 different anion-protein interaction sites were identified on the surfaces of cytochrome c, 10 of which were found in both forms, 8 present only in the oxidized and 8 only in the reduced form. The structural analysis of the electron transfer complexes, based on this new information, suggests a specific exit strategy for cytochrome c after formation of productive protein-protein complexes: a directional sliding mechanism for the electron shuttle on the surface of the redox partner is proposed to take place after the electron transfer process has occurred. Copyright © 2014 Elsevier Inc. All rights reserved.

Redox thermodynamics of the native and alkaline forms of eukaryotic and bacterial class I cytochromes c.

Science.gov (United States)

Battistuzzi, G; Borsari, M; Sola, M; Francia, F

1997-12-23

The reduction potentials of beef heart cytochrome c and cytochromes c2 from Rhodopseudomonas palustris, Rhodobacter sphaeroides, and Rhodobacter capsulatus were measured through direct electrochemistry at a surface-modified gold electrode as a function of temperature in nonisothermal experiments carried out at neutral and alkaline pH values. The thermodynamic parameters for protein reduction (DeltaS degrees rc and DeltaH degrees rc) were determined for the native and alkaline conformers. Enthalpy and entropy terms underlying species-dependent differences in E degrees and pH- and temperature-induced E degrees changes for a given cytochrome were analyzed. The difference of about +0.1 V in E degrees between cytochromes c2 and the eukaryotic species can be separated into an enthalpic term (-DeltaDeltaH degrees rc/F) of +0.130 V and an entropic term (TDeltaDeltaS degrees rc/F) of -0.040 V. Hence, the higher potential of the bacterial species appears to be determined entirely by a greater enthalpic stabilization of the reduced state. Analogously, the much lower potential of the alkaline conformer(s) as compared to the native species is by far enthalpic in origin for both protein families, and is largely determined by the substitution of Met for Lys in axial heme ligation. Instead, the biphasic E degrees /temperature profile for the native cytochromes is due to a difference in reduction entropy between the conformers at low and high temperatures. Temperature-dependent 1H NMR experiments suggest that the temperature-induced transition also involves a change in orientation of the axial methionine ligand with respect to the heme plane.

Theoretical analysis of the domain-swapped dimerization of cytochrome c: An MD and 3D-RISM approach

Science.gov (United States)

Yoshida, Norio; Higashi, Masahiro; Motoki, Hideyoshi; Hirota, Shun

2018-01-01

The structural stability of a cytochrome c domain-swapped dimer compared with that of the monomer was investigated by molecular dynamics (MD) simulations and by three-dimensional reference interaction site model (3D-RISM) theory. The structural fluctuation and structural energy of cytochrome c were treated by MD simulations, and the solvation thermodynamics was treated by 3D-RISM theory. The domain-swapped dimer state is slightly less stable than the monomer state, which is consistent with experimental observations; the total free energy difference is calculated as 25 kcal mol-1. The conformational change and translational/rotational entropy change contribute to the destabilization of the dimer, whereas the hydration and vibrational entropy contribute to the stabilization. Further analyses on the residues located at the hinge loop for swapping were conducted, and the results reveal details at the molecular level of the structural and interaction changes upon dimerization.

Basic features of the pion valence-quark distribution function

Energy Technology Data Exchange (ETDEWEB)

Chang, Lei [CSSM, School of Chemistry and Physics, University of Adelaide, Adelaide, SA 5005 (Australia); Mezrag, Cédric; Moutarde, Hervé [Centre de Saclay, IRFU/Service de Physique Nucléaire, F-91191 Gif-sur-Yvette (France); Roberts, Craig D. [Physics Division, Argonne National Laboratory, Argonne, IL 60439 (United States); Rodríguez-Quintero, Jose [Departamento de Física Aplicada, Facultad de Ciencias Experimentales, Universidad de Huelva, Huelva E-21071 (Spain); Tandy, Peter C. [Center for Nuclear Research, Department of Physics, Kent State University, Kent, OH 44242 (United States)

2014-10-07

The impulse-approximation expression used hitherto to define the pion's valence-quark distribution function is flawed because it omits contributions from the gluons which bind quarks into the pion. A corrected leading-order expression produces the model-independent result that quarks dressed via the rainbow–ladder truncation, or any practical analogue, carry all the pion's light-front momentum at a characteristic hadronic scale. Corrections to the leading contribution may be divided into two classes, responsible for shifting dressed-quark momentum into glue and sea-quarks. Working with available empirical information, we use an algebraic model to express the principal impact of both classes of corrections. This enables a realistic comparison with experiment that allows us to highlight the basic features of the pion's measurable valence-quark distribution, q{sup π}(x); namely, at a characteristic hadronic scale, q{sup π}(x)∼(1−x){sup 2} for x≳0.85; and the valence-quarks carry approximately two-thirds of the pion's light-front momentum.

Spectroscopic determination of valence band parameters in InP

International Nuclear Information System (INIS)

Lewis, R.A.; Lough, B.C.C.

2003-01-01

Full text: The general form of the Hamiltonian for an electron or hole in a semiconductor has been given by Luttinger. The valence band is characterised by three parameters - γ 1 , γ 2 , γ 3 -now commonly known as the Luttinger parameters. Despite many investigations there is still considerable uncertainty regarding the Luttinger parameters of InP. The situation has been reviewed by Hackenberg et al. These authors themselves sought to determine the Luttinger parameters by hot-electron luminescence and discovered that many Luttinger parameter triplets were consistent with their data. We employ a spectroscopic approach to estimating valence-band parameters in InP. Calculations have been made for both the unperturbed energy levels and the energy levels in a magnetic field of acceptor impurities in semiconductors characterised by different Luttinger parameters. We compare our recent experimental data for the transitions associated with the Zn acceptor impurity in InP in magnetic fields up to 30 T to determine the most appropriate set of valence-band parameters for InP

Thermodynamics and kinetics of reduction and species conversion at a hydrophobic surface for mitochondrial cytochromes c and their cardiolipin adducts

International Nuclear Information System (INIS)

Ranieri, Antonio; Di Rocco, Giulia; Millo, Diego; Battistuzzi, Gianantonio; Bortolotti, Carlo A.; Lancellotti, Lidia; Borsari, Marco; Sola, Marco

2015-01-01

Highlights: • Cytochrome c and its adduct with cardiolipin can be immobilized on a hydrophobic SAM. • Adsorbed cytochrome c and its adduct undergo extensive unfolding and axial ligand substitution. • An equilibrium between a six-coordinated and a five-coordinated form is observed in both cases. • The reduced five-coordinated form is stabilized by cardiolipin binding. • Immobilized cytochrome c exchanges electrons more slowly upon cardiolipin binding. - Abstract: Cytochrome c (cytc) and its adduct with cardiolipin (CL) were immobilized on a hydrophobic SAM-coated electrode surface yielding a construct which mimics the environment experienced by the complex at the inner mitochondrial membrane where it plays a role in cell apoptosis. Under these conditions, both species undergo an equilibrium between a six-coordinated His/His-ligated and a five-coordinated His/- ligated forms stable in the oxidized and in the reduced state, respectively. The thermodynamics of the oxidation-state dependent species conversion were determined by temperature-dependent diffusionless voltammetry experiments. CL binding stabilizes the immobilized reduced His/- ligated form of cytc which was found previously to catalytically reduce dioxygen. Here, this adduct is also found to show pseudoperoxidase activity, catalysing reduction of hydrogen peroxide. These effects would impart CL with an additional role in the cytc-mediated peroxidation leading to programmed cell death. Moreover, immobilized cytc exchanges electrons more slowly upon CL binding possibly due to changes in solvent reorganization effects at the protein-SAM interface

Effects of Magnetic Field on the Valence Bond Property of the Double-Quantum-Dot Molecule

Institute of Scientific and Technical Information of China (English)

王立民; 罗莹; 马本堃

2002-01-01

The effects of the magnetic field on the valence bond property of the double-quantum-dot molecule are numerically studied by the finite element method and perturbation approach because of the absence of cylindrical symmetry in the horizontally coupled dots. The calculation results show that the energy value of the ground state changes differently from that of the first excited state with increasing magnetic field strength, and they cross under a certain magnetic field. The increasing magnetic field makes the covalent bond state change into an ionic bond state, which agrees qualitatively with experimental results and makes ionic bond states remain. The oscillator strength of transition between covalent bond states decreases distinctly with the increasing magnetic field strength, when the molecule is irradiated by polarized light. Such a phenomenon is possibly useful for actual applications.

Conduction Mechanism of Valence Change Resistive Switching Memory: A Survey

Directory of Open Access Journals (Sweden)

Ee Wah Lim

2015-09-01

Full Text Available Resistive switching effect in transition metal oxide (TMO based material is often associated with the valence change mechanism (VCM. Typical modeling of valence change resistive switching memory consists of three closely related phenomena, i.e., conductive filament (CF geometry evolution, conduction mechanism and temperature dynamic evolution. It is widely agreed that the electrochemical reduction-oxidation (redox process and oxygen vacancies migration plays an essential role in the CF forming and rupture process. However, the conduction mechanism of resistive switching memory varies considerably depending on the material used in the dielectric layer and selection of electrodes. Among the popular observations are the Poole-Frenkel emission, Schottky emission, space-charge-limited conduction (SCLC, trap-assisted tunneling (TAT and hopping conduction. In this article, we will conduct a survey on several published valence change resistive switching memories with a particular interest in the I-V characteristic and the corresponding conduction mechanism.

A facilitative effect of negative affective valence on working memory.

Science.gov (United States)

Gotoh, Fumiko; Kikuchi, Tadashi; Olofsson, Ulrich

2010-06-01

Previous studies have shown that negatively valenced information impaired working memory performance due to an attention-capturing effect. The present study examined whether negative valence could also facilitate working memory. Affective words (negative, neutral, positive) were used as retro-cues in a working memory task that required participants to remember colors at different spatial locations on a computer screen. Following the cue, a target detection task was used to either shift attention to a different location or keep attention at the same location as the retro-cue. Finally, participants were required to discriminate the cued color from a set of distractors. It was found that negative cues yielded shorter response times (RTs) in the attention-shift condition and longer RTs in the attention-stay condition, compared with neutral and positive cues. The results suggest that negative affective valence may enhance working memory performance (RTs), provided that attention can be disengaged.

Fe II/Fe III mixed-valence state induced by Li-insertion into the metal-organic-framework Mil53(Fe): A DFT+U study

Science.gov (United States)

Combelles, C.; Ben Yahia, M.; Pedesseau, L.; Doublet, M.-L.

The iron-based metal-organic-framework MIL53(Fe) has recently been tested as a cathode materials for Li-Ion batteries, leading to promising cycling life and rate capability. Despite a poor capacity of 70 mAh g -1 associated with the exchange of almost 0.5Li/Fe, this result is the first evidence of a reversible lithium insertion never observed in a MOF system. In the present study, the MIL53(Fe) redox mechanism is investigated through first-principles DFT+U calculations. The results show that MIL53(Fe) is a weak antiferromagnetic charge transfer insulator at T = 0 K, with iron ions in the high-spin S = 5/2 state. Its reactivity vs elemental lithium is then investigated as a function of lithium composition and distribution over the most probable Li-sites of the MOF structure. The redox mechanism is fully interpreted as a two-step insertion/conversion mechanism, associated with the stabilization of the Fe 3+/Fe 2+ mixed-valence state prior to the complete decomposition of the inorganic-organic interactions within the porous MOF architecture.

The amino acid sequence of cytochrome c from Cucurbita maxima L. (pumpkin)

Science.gov (United States)

Thompson, E. W.; Richardson, M.; Boulter, D.

1971-01-01

The amino acid sequence of pumpkin cytochrome c was determined on 2μmol of protein. Some evidence was found for the occurrence of two forms of cytochrome c, whose sequences differed in three positions. Pumpkin cytochrome c consists of 111 residues and is homologous with mitochondrial cytochromes c from other plants. Experimental details are given in a supplementary paper that has been deposited as Supplementary Publication SUP 50005 at the National Lending Library for Science and Technology, Boston Spa, Yorks. LS23 7BQ, U.K., from whom copies can be obtained on the terms indicated in Biochem. J. (1971), 121, 7. PMID:5131733

Aspirin Induces Apoptosis through Release of Cytochrome c from Mitochondria

Directory of Open Access Journals (Sweden)

Katja C. Zimmermann

2000-01-01

Full Text Available Nonsteroidal anti-inflammatory drugs (NSAID reduce the risk for cancer, due to their anti proliferative and apoptosis-inducing effects. A critical pathway for apoptosis involves the release of cytochrome c from mitochondria, which then interacts with Apaf-1 to activate caspase proteases that orchestrate cell death. In this study we found that treatment of a human cancer cell line with aspirin induced caspase activation and the apoptotic cell morphology, which was blocked by the caspase inhibitor zVAD-fmk. Further analysis of the mechanism underlying this apoptotic event showed that aspirin induces translocation of Bax to the mitochondria and triggers release of cytochrome c into the cytosol. The release of cytochrome c from mitochondria was inhibited by overexpression of the antiapoptotic protein Bcl-2 and cells that lack Apaf-1 were resistant to aspirin-induced apoptosis. These data provide evidence that the release of cytochrome c is an important part of the apoptotic mechanism of aspirin.

Dipole-bound states as doorways in (dissociative) electron attachment

International Nuclear Information System (INIS)

Sommerfeld, Thomas

2005-01-01

This communication starts with a comparison of dissociative recombination and dissociative attachment placing emphasis on the role of resonances as reactive intermediates. The main focus is then the mechanism of electron attachment to polar molecules at very low energies (100 meV). The scheme considered consists of two steps: First, an electron is captured in a diffuse dipole-bound state depositing its energy in the vibrational degrees of freedom, in other words, a vibrational Feshbach resonance is formed. Then, owing to the coupling with a valence state, the electron is transferred into a compact valence orbital, and depending on the electron affinities of the valence state and possible dissociation products, as well as on the details of the intramolecular redistribution of vibrational energy, long-lived anions can be generated or dissociation reactions can be initiated. The key property in this context is the electronic coupling strength between the diffuse dipole-bound and the compact valence states. We describe how the coupling strength can be extracted from ab initio data, and present results for Nitromethane, Uracil and Cyanoacetylene

Spin Dynamics and Magnetic Ordering in Mixed Valence Systems

DEFF Research Database (Denmark)

Shapiro, S. M.; Bjerrum Møller, Hans; Axe, J. D.

1978-01-01

. 0 meV at the transition to the alpha phase. The temperature independence of the susceptibility within the gamma phase cannot be simply reconciled with the temperature dependence of the valence within the gamma phase. TmSe is shown to order in a type I antiferromagnetic structure below T//N similar 3....... 2 K. The magnetic phase diagram is understood as a successive domain reorientation and a metamagnetic phase transition for T less than 3 K with increasing field. The mixed valence nature manifests itself in a reduced moment and a markedly altered crystal field. Another sample of TmSe with a lattice...

Graduate radiographers' expectations for role development - The potential impact of misalignment of expectation and valence on staff retention and service provision

Energy Technology Data Exchange (ETDEWEB)

Williamson, Keren [Department of Radiography, School of Healthcare Studies, Cardiff University, Heath Park, Cardiff CF14 4XN (United Kingdom)], E-mail: williamsonk2@cardiff.ac.uk; Mundy, Lynn A. [Department of Radiography, School of Healthcare Studies, Cardiff University, Heath Park, Cardiff CF14 4XN (United Kingdom)

2010-02-15

Purpose: The purpose of this study was to investigate the role development expectations of graduate radiographers with a view to predicting the potential impact of a misalignment of these expectations and valence on service delivery and staff retention. A final year cohort of radiography students completed a questionnaire designed to explore topics associated with role development opportunities. Method: Structured questionnaires, in the Likert scale format, utilised 20 attitude questions constructed to elicit information in relation to 3 main themes of investigation; expectation, valence and knowledge. Results: All participants (n = 37) stated an expectation for role development opportunities with 97.3% (n = 36) indicating that these expectations would be realised within 5 years of graduation and 75.7% (n = 28) within 2 years of graduation. A significant correlation between expectation for role development and job satisfaction was seen (p < 0.05). 81.1% (n = 30) of participants stated turnover intentions in order to meet their expectations. Conclusion: There is an expectation for role development opportunities for new graduates with a valence noted of the intrinsic reward of meeting these expectations. Expectation and valence are seen to be intrinsically linked with job satisfaction suggesting that misalignment of these would have a potentially negative impact on motivation and retention of the future radiography workforce demonstrating a positive correlation with withdrawal behaviours, including turnover intentions. In a relatively small professional group such as radiography the phenomenon of group cohesion may be strong suggesting that withdrawal behaviours may manifest as 'resignation in post', impacting on the quality of care and service provision for patients.

SDS-facilitated in vitro formation of a transmembrane B-type cytochrome is mediated by changes in local pH

DEFF Research Database (Denmark)

Weber, M.; Schneider, D.; Prodöhl, A.

2011-01-01

cytochrome b(559)', which can be efficiently assembled in vitro from a heme-binding PsbF homo-dimer by combining free heme with the apo-cytochrome b(559)'. Unfolding of the protein dissolved in the mild detergent dodecyl maltoside may be induced by addition of SDS, which at high concentrations leads to dimer...... dissociation. Surprisingly, absorption spectroscopy reveals that heme binding and cytochrome formation at pH 8.0 are optimal at intermediate SDS concentrations. Stopped-flow kinetics revealed that genuine conformational changes are involved in heme binding at these SDS concentrations. GPS (Global Protein...... folding State mapping) NMR measurements showed that optimal heme binding is intimately related to a change in the degree of histidine protonation. In the absence of SDS, the pH curve for heme binding is bell-shaped with an optimum at around pH 6-7. At alkaline pH values, the negative electrostatic...

Framing Prisoners and Chickens: Valence Effects in the Prisoner's Dilemma and the Chicken Game

OpenAIRE

De Heus , Peter; Hoogervorst , Niek; Van Dijk , Eric

2010-01-01

International audience; In an experimental study we investigated how decisions in social dilemmas are affected by the valence of outcomes that are at stake. Prospect theory states that individuals are risk averse when outcomes are framed as gains, and risk seeking when outcomes are framed as losses. On the basis of this framework, previous research on social dilemmas has addressed the question of whether people are more cooperative in the negative domain than in the positive domain, but this ...

A web-based resource for the Arabidopsis P450, cytochromes b5, NADPH-cytochrome P450 reductases, and family 1 glycosyltransferases (http://www.P450.kvl.dk).

Science.gov (United States)

Paquette, Suzanne M; Jensen, Kenneth; Bak, Søren

2009-12-01

Gene and genome duplication is a key driving force in evolution of plant diversity. This has resulted in a number of large multi-gene families. Two of the largest multi-gene families in plants are the cytochromes P450 (P450s) and family 1 glycosyltransferases (UGTs). These two families are key players in evolution, especially of plant secondary metabolism, and in adaption to abiotic and biotic stress. In the model plant Arabidopsis thaliana there are 246 and 112 cytochromes P450 and UGTs, respectively. The Arabidopsis P450, cytochromes b(5), NADPH-cytochrome P450 reductases, and family 1 glycosyltransferases website (http://www.P450.kvl.dk) is a sequence repository of manually curated sequences, multiple sequence alignments, phylogenetic trees, sequence motif logos, 3D structures, intron-exon maps, and customized BLAST datasets.

Variable valence of praseodymium in rare-earth oxide solid solutions

International Nuclear Information System (INIS)

Kravchinskaya, M.V.; Merezhinskii, K.Y.; Tikhonov, P.A.

1986-01-01

Solid solutions of elevated praseodymium oxide content have interesting electrical properties, making them the basis for the manufacture of high-temperature electrically conducting materials. Establishment of the composition-structure-valence state relationships enables control of the material properties. The authors performed investigations using a thermogravimetric apparatus with an electronic microbalance of type EM-5-3M, and using x-ray phase analysis of powders (DRON-1 diffractometer, CuK /SUB alpha/ -radiation). The authors also studied the kinetics of praseodymium oxidation with a thermogravimetric apparatus under isothermal conditions. Evaluation of the results with the equation of Kolmogorov, Erofeev, and Avraam indicates that the process is limited by the chemical oxidation of praseodymium and not by diffusion

Individual differences in emotion-cognition interactions: Emotional valence interacts with serotonin transporter genotype to influence brain systems involved in emotional reactivity and cognitive control

Directory of Open Access Journals (Sweden)

Melanie eStollstorff

2013-07-01

Full Text Available The serotonin transporter gene (5-HTTLPR influences emotional reactivity and attentional bias towards or away from emotional stimuli and has been implicated in psychopathological states, such as depression and anxiety disorder. The short allele is associated with increased reactivity and attention towards negatively-valenced emotional information, whereas the long allele is associated with that towards positively-valenced emotional information. The neural basis for individual differences in the ability to exert cognitive control over these bottom-up biases in emotional reactivity and attention is unknown, an issue investigated in the present study. Two groups, homozygous 5-HTTLPR long allele carriers or homozygous short allele carriers, underwent functional magnetic resonance imaging (fMRI while completing an Emotional Stroop-like task that varied with regards to the congruency of task-relevant and task-irrelevant information and the emotional valence of the task-irrelevant information. Behaviorally, participants demonstrated the classic Stroop effect (slower responses for incongruent than congruent trials, which did not differ by 5-HTTLPR genotype. However, fMRI results revealed that genotype influenced the degree to which neural systems were engaged depending on the valence of the conflicting task-irrelevant information. While the Long group recruited prefrontal control regions and superior temporal sulcus during conflict when task-irrelevant information was positively-valenced, the "Short" group recruited these regions when task-irrelevant information was negatively-valenced. Thus, participants successfully engaged cognitive control to overcome conflict in an emotional context using similar neural circuitry, but the engagement of this circuitry depended on emotional valence and 5-HTTLPR status. These results suggest that the interplay between emotion and cognition is modulated, in part, by a genetic polymorphism that influences serotonin

On the electrical conductivity for the mixed-valence model with d-f correlations

International Nuclear Information System (INIS)

Borgiel, W.; Matlak, M.

1984-08-01

The static electrical conductivity of mixed-valence systems is calculated in the model of Matlak and Nolting [Solid State Commun., 47, 11 (1983); Z. Phys., B55, 103 (1984)]. The method takes into account the atomic properties more exactly than those connected with bands, and hence emphasizes the ionic aspect of the problem in some way; indeed, the calculations overestimate the atomic properties. Some results are presented in a graph. It is found that the electrical conductivity depends strongly on temperature and the electron-hole attraction constant

Cytochrome c and c1 heme lyases are essential in Plasmodium berghei.

Science.gov (United States)

Posayapisit, Navaporn; Songsungthong, Warangkhana; Koonyosying, Pongpisid; Falade, Mofolusho O; Uthaipibull, Chairat; Yuthavong, Yongyuth; Shaw, Philip J; Kamchonwongpaisan, Sumalee

Malaria parasites possess a de novo heme synthetic pathway. Interestingly, this pathway is dispensable during the blood stages of development in mammalian hosts. The assembly of the two most important hemeproteins, cytochromes c and c1, is mediated by cytochrome heme lyase enzymes. Plasmodium spp. possess two cytochrome heme lyases encoded by separate genes. Given the redundancy of heme synthesis, we sought to determine if heme lyase function also exhibits redundancy. To answer this question, we performed gene knockout experiments. We found that the PBANKA_143950 and PBANKA_0602600 Plasmodium berghei genes encoding cytochrome c (Pbcchl) and cytochrome c1 (Pbcc 1 hl) heme lyases, respectively, can only be disrupted when a complementary gene is present. In contrast, four genes in the de novo heme synthesis pathway can be disrupted without complementation. This work provides evidence that Pbcchl and Pbcc 1 hl are both essential and thus may be antimalarial targets. Copyright © 2016 Elsevier B.V. All rights reserved.

Evaluation of cytochrome P-450 concentration in Saccharomyces cerevisiae strains

Directory of Open Access Journals (Sweden)

Míriam Cristina Sakuragui Matuo

2010-09-01

Full Text Available Saccharomyces cerevisiae has been widely used in mutagenicity tests due to the presence of a cytochrome P-450 system, capable of metabolizing promutagens to active mutagens. There are a large number of S. cerevisiae strains with varying abilities to produce cytochrome P-450. However, strain selection and ideal cultivation conditions are not well defined. We compared cytochrome P-450 levels in four different S. cerevisiae strains and evaluated the cultivation conditions necessary to obtain the highest levels. The amount of cytochrome P-450 produced by each strain varied, as did the incubation time needed to reach the maximum level. The highest cytochrome P-450 concentrations were found in media containing fermentable sugars. The NCYC 240 strain produced the highest level of cytochrome P-450 when grown in the presence of 20 % (w/v glucose. The addition of ethanol to the media also increased cytochrome P-450 synthesis in this strain. These results indicate cultivation conditions must be specific and well-established for the strain selected in order to assure high cytochrome P-450 levels and reliable mutagenicity results.Linhagens de Saccharomyces cerevisiae tem sido amplamente empregadas em testes de mutagenicidade devido à presença de um sistema citocromo P-450 capaz de metabolizar substâncias pró-mutagênicas à sua forma ativa. Devido à grande variedade de linhagens de S. cerevisiae com diferentes capacidades de produção de citocromo P-450, torna-se necessária a seleção de cepas, bem como a definição das condições ideais de cultivo. Neste trabalho, foram comparados os níveis de citocromo P-450 em quatro diferentes linhagens de S. cerevisiae e avaliadas as condições de cultivo necessárias para obtenção de altas concentrações deste sistema enzimático. O maior nível enzimático foi encontrado na linhagem NCYC 240 em presença de 20 % de glicose (p/v. A adição de etanol ao meio de cultura também produziu um aumento na s

Cardiolipin modulates allosterically peroxynitrite detoxification by horse heart cytochrome c

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Ascenzi, Paolo, E-mail: ascenzi@uniroma3.it [Department of Biology and Interdepartmental Laboratory for Electron Microscopy, University Roma Tre, I-00146 Roma (Italy); Ciaccio, Chiara [Department of Experimental Medicine and Biochemical Sciences, University of Roma ' Tor Vergata' , I-00133 Roma (Italy); Interuniversity Consortium for the Research on the Chemistry of Metals in Biological Systems, I-70126 Bari (Italy); Sinibaldi, Federica; Santucci, Roberto [Department of Experimental Medicine and Biochemical Sciences, University of Roma ' Tor Vergata' , I-00133 Roma (Italy); Coletta, Massimo [Department of Experimental Medicine and Biochemical Sciences, University of Roma ' Tor Vergata' , I-00133 Roma (Italy); Interuniversity Consortium for the Research on the Chemistry of Metals in Biological Systems, I-70126 Bari (Italy)

2011-01-07

Research highlights: {yields} Cardiolipin binding to cytochrome c. {yields} Cardiolipin-dependent peroxynitrite isomerization by cytochrome c. {yields} Cardiolipin-cytochrome c complex plays pro-apoptotic effects. {yields} Cardiolipin-cytochrome c complex plays anti-apoptotic effects. -- Abstract: Upon interaction with bovine heart cardiolipin (CL), horse heart cytochrome c (cytc) changes its tertiary structure disrupting the heme-Fe-Met80 distal bond, reduces drastically the midpoint potential out of the range required for its physiological role, binds CO and NO with high affinity, and displays peroxidase activity. Here, the effect of CL on peroxynitrite isomerization by ferric cytc (cytc-Fe(III)) is reported. In the absence of CL, hexa-coordinated cytc does not catalyze peroxynitrite isomerization. In contrast, CL facilitates cytc-Fe(III)-mediated isomerization of peroxynitrite in a dose-dependent fashion inducing the penta-coordination of the heme-Fe(III)-atom. The value of the second order rate constant for CL-cytc-Fe(III)-mediated isomerization of peroxynitrite (k{sub on}) is (3.2 {+-} 0.4) x 10{sup 5} M{sup -1} s{sup -1}. The apparent dissociation equilibrium constant for CL binding to cytc-Fe(III) is (5.1 {+-} 0.8) x 10{sup -5} M. These results suggest that CL-cytc could play either pro-apoptotic or anti-apoptotic effects facilitating lipid peroxidation and scavenging of reactive nitrogen species, such as peroxynitrite, respectively.

Oleamide synthesizing activity from rat kidney: identification as cytochrome c.

Science.gov (United States)

Driscoll, William J; Chaturvedi, Shalini; Mueller, Gregory P

2007-08-03

Oleamide (cis-9-octadecenamide) is the prototype member of an emerging class of lipid signaling molecules collectively known as the primary fatty acid amides. Current evidence suggests that oleamide participates in the biochemical mechanisms underlying the drive to sleep, thermoregulation, and antinociception. Despite the potential importance of oleamide in these physiologic processes, the biochemical pathway for its synthesis in vivo has not been established. We report here the discovery of an oleamide synthetase found in rat tissues using [(14)C]oleoyl-CoA and ammonium ion. Hydrogen peroxide was subsequently found to be a required cofactor. The enzyme displayed temperature and pH optima in the physiologic range, a remarkable resistance to proteolysis, and specificity for long-chain acyl-CoA substrates. The reaction demonstrated Michaelis-Menten kinetics with a K(m) for oleoyl-CoA of 21 microm. Proteomic, biochemical, and immunologic analyses were used to identify the source of the oleamide synthesizing activity as cytochrome c. This identification was based upon peptide mass fingerprinting of isolated synthase protein, a tight correlation between enzymatic activity and immunoreactivity for cytochrome c, and identical functional properties shared by the tissue-derived synthetase and commercially obtained cytochrome c. The ability of cytochrome c to catalyze the formation of oleamide experimentally raises the possibility that cytochrome c may mediate oleamide biosynthesis in vivo.

Geometrical analysis of cytochrome c unfolding

Science.gov (United States)

Urie, Kristopher G.; Pletneva, Ekaterina; Gray, Harry B.; Winkler, Jay R.; Kozak, John J.

2011-01-01

A geometrical model has been developed to study the unfolding of iso-1 cytochrome c. The model draws on the crystallographic data reported for this protein. These data were used to calculate the distance between specific residues in the folded state, and in a sequence of extended states defined by n = 3, 5, 7, 9, 11, 13, and 15 residue units. Exact calculations carried out for each of the 103 residues in the polypeptide chain demonstrate that different regions of the chain have different unfolding histories. Regions where there is a persistence of compact structures can be identified, and this geometrical characterization is fully consistent with analyses of time-resolved fluorescence energy-transfer (TrFET) data using dansyl-derivatized cysteine side-chain probes at positions 39, 50, 66, 85, and 99. The calculations were carried out assuming that different regions of the polypeptide chain unfold synchronously. To test this assumption, lattice Monte Carlo simulations were performed to study systematically the possible importance of asynchronicity. Calculations show that small departures from synchronous dynamics can arise if displacements of residues in the main body of the chain are much more sluggish than near-terminal residues.

A study on the interaction of horse heart cytochrome c with some conventional and ionic liquid surfactants probed by ultraviolet-visible and fluorescence spectroscopic techniques

Science.gov (United States)

Mondal, Satyajit; Das, Bijan

2018-06-01

The interactions of a protein cytochrome c with some selected conventional and ionic liquid surfactants have been investigated at pH 7.4 using ultraviolet-visible and fluorescence spectroscopic techniques. We used four conventional surfactants - cetyltrimethylammonium bromide (CTAB), dodecyltrimethylammonium bromide (DTAB), sodium N-dodecanoylsarcosinate (SDDS), and N-decanoyl-N-methylglucamine (Mega 10), and a surface active ionic liquid 1-hexadecyl-3-methylimidazolium chloride (C16MeImCl). All the investigated surfactants were found to induce an unfolding of the protein cytochrome c. In presence of CTAB, SDDS and C16MeImCl, the heme iron atom was found to loose methionine from its axial position. Differential binding of the surfactant monomers and their micelles to the protein molecules was inferred. The ionic surfactants were found to be more effective than the nonionic one in unfolding the investigated protein. However, the extent of binding of CTAB/C16MeImCl to cytochrome c reaches a plateau past the critical micellization concentration (cmc) of the surfactant. For each of the cytochrome c-DTAB, cytochrome c-SDDS and cytochrome c-Mega 10 system, although there exists an inflection in the surfactant-binding, saturation point could not be detected. It has been demonstrated from the ultraviolet-visible spectral studies that the oxidation state of iron in cytochrome c does not change when the protein binds with the investigated surfactants.

Evaluative conditioning induces changes in sound valence

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Anna C. Bolders

2012-04-01

Full Text Available Evaluative Conditioning (EC has hardly been tested in the auditory domain, but it is a potentially valuable research tool. In Experiment 1 we investigated whether the affective evaluation of short environmental sounds can be changed using affective words as unconditioned stimuli (US. Congruence effects on an affective priming task (APT for conditioned sounds demonstrated successful EC. Subjective ratings for sounds paired with negative words changed accordingly. In Experiment 2 we investigated whether the acquired valence remains stable after repeated presentation of the conditioned sound without the US or whether extinction occurs. The acquired affective value remained present, albeit weaker, even after 40 extinction trials. These results warrant the use of EC to study processing of short environmental sounds with acquired valence, even if this requires repeated stimulus presentations. This paves the way for studying processing of affective environmental sounds while effectively controlling low level-stimulus properties.

Beyond Valence and Magnitude: a Flexible Evaluative Coding System in the Brain

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Gu, Ruolei; Lei, Zhihui; Broster, Lucas; Wu, Tingting; Jiang, Yang; Luo, Yue-jia

2013-01-01

Outcome evaluation is a cognitive process that plays an important role in our daily lives. In most paradigms utilized in the field of experimental psychology, outcome valence and outcome magnitude are the two major features investigated. The classical “independent coding model” suggest that outcome valence and outcome magnitude are evaluated by separate neural mechanisms that may be mapped onto discrete event-related potential (ERP) components: feedback-related negativity (FRN) and the P3, respectively. To examine this model, we presented outcome valence and magnitude sequentially rather than simultaneously. The results reveal that when only outcome valence or magnitude is known, both the FRN and the P3 encode that outcome feature; when both aspects of outcome are known, the cognitive functions of the two components dissociate: the FRN responds to the information available in the current context, while the P3 pattern depends on outcome presentation sequence. The current study indicates that the human evaluative system, indexed in part by the FRN and the P3, is more flexible than previous theories suggested. PMID:22019775

THREE-VALENCE-PARTICE NUCLEI IN THE 132Sn and 208 Pb REGIONS

International Nuclear Information System (INIS)

Benchikh, L.; Draoui, B.; Latfaoui, M.; Aissaoui, L.

2011-01-01

Full text: Among the nuclei of the nuclear charter, the nuclei around closed shells play a key role in understanding the effective interaction properties between nucleons far from the valley of stability; particulary, the nuclei of a few valence nucleons around doubly magic 208 28Pb126 and 132 50Sn82 nuclei. The interest of both regions 208Pb and 132Sn lies in the fact that there is a great similarity between their nuclear spectroscopic properties. The single energy gaps in both cases are comparable and the orbitals above and below these gaps are similarly ordered. Each single state in the region of 132Sn has its counterpart in that of 208Pb. An interesting predictive consequence, the interactions of the Sn region, difficult region to reach experimentally, can be estimated from their corresponding ones constructed to describe the nuclei of the Pb region. Because of the importance of the similarity existing between the spectroscopy of these two regions, we are interested in nuclei with three valence nucleons in the lead and Tin regions on the basis of experimental data (spin, parity and energy states). In this context, the theoretical study is conducted within the shell model using the MSDI interaction for the energy spectra calculations of the studied nuclei. The calculated results are in good agreement with the available experimental data and show evidence that a close resemblance between the spectroscopy of these two regions persists when moving away from the immediate neighbours of doubly magic 132Sn and 208Pb.

Nitrate as a probe of cytochrome c surface : crystallographic identification of crucial "hot spots" for protein-protein recognition

NARCIS (Netherlands)

De March, Matteo; Demitri, Nicola; De Zorzi, Rita; Casini, Angela; Gabbiani, Chiara; Guerri, Annalisa; Messori, Luigi; Geremia, Silvano

The electrostatic surface of cytochrome c and its changes with the iron oxidation state are involved in the docking and undocking processes of this protein to its biological partners in the mitochondrial respiratory pathway. To investigate the subtle mechanisms of formation of productive

Electronic structures and valence band splittings of transition metals doped GaNs

International Nuclear Information System (INIS)

Lee, Seung-Cheol; Lee, Kwang-Ryeol; Lee, Kyu-Hwan

2007-01-01

For a practical viewpoint, presence of spin splitting of valence band in host semiconductors by the doping of transition metal (TM) ions is an essential property when designing a diluted magnetic semiconductors (DMS) material. The first principle calculations were performed on the electronic and magnetic structure of 3d transition metal doped GaN. V, Cr, and Mn doped GaNs could not be candidates for DMS materials since most of their magnetic moments is concentrated on the TM ions and the splittings of valence band were negligible. In the cases of Fe, Co, Ni, and Cu doped GaNs, on the contrary, long-ranged spin splitting of valence band was found, which could be candidates for DMS materials

Age effects in emotional prospective memory: cue valence differentially affects the prospective and retrospective component.

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Schnitzspahn, Katharina M; Horn, Sebastian S; Bayen, Ute J; Kliegel, Matthias

2012-06-01

While first studies suggested that emotional task material may enhance prospective memory performance in young and older adults, the extent and mechanisms of this effect are under debate. The authors explored possible differential effects of cue valence on the prospective and retrospective component of prospective memory in young and older adults. Forty-five young and 41 older adults performed a prospective memory task in which emotional valence of the prospective memory cue was manipulated (positive, negative, neutral). The multinomial model of event-based prospective memory was used to analyze effects of valence and age on the two prospective memory components separately. Results revealed an interaction indicating that age differences were smaller in both emotional valence conditions. For older adults positive cues improved the prospective component, while negative cues improved the retrospective component. No main effect of valence was found for younger adults on an overt accuracy measure, but model-based analyses showed that the retrospective component was enhanced in the positive compared with the negative cue condition. The study extends the literature in demonstrating that processes underlying emotional effects on prospective memory may differ depending on valence and age. PsycINFO Database Record (c) 2012 APA, all rights reserved

Valency and spin states of substituent cations in Bi2.15Sr1.85CaCu2O8+δ

Science.gov (United States)

Benseman, T. M.; Cooper, J. R.; Zentile, C. L.; Lemberger, L.; Balakrishnan, G.

2011-10-01

We studied the valency and spin behavior of M = Mn, Fe, Co, Li, and Al in the high-temperature superconducting compound Bi2.15Sr1.85Ca(Cu1-zMz)2O8+δ (Bi-2212) for small values of z. Mn, Fe, and Co retain their magnetic moments, and our thermopower and magnetic susceptibility data imply ionization states Mn3+, Fe2+, and Co2+, while Li and Al are accommodated in the charge reservoir layers. Single-crystal studies show that the susceptibility of Co2+ ions in Bi-2212 is strongly anisotropic, with a weak anisotropy detected for Mn3+ and none for Fe2+. Fits to a pseudogap formula for a pure Bi-2212 crystal suggest that the spin susceptibility of the host compound is more anisotropic than previously realized. Data in the superconducting state allow us to compare the pair-breaking properties of the different impurities. Several aspects of the data, including the stronger suppression of the superconducting transition temperature Tc by Co compared with Fe for underdoped and optimally doped samples, show that the d-level structure of the magnetic ions and multiorbital effects are important. We also find that the temperatures of the magnetization crossing points are equal to the low-field Tc values to within 1% or 2%. This agrees with a 2D thermodynamic fluctuation argument given by Junod

Persistent low-temperature spin dynamics in the mixed-valence iridate Ba3InIr2O9

Science.gov (United States)

Dey, Tusharkanti; Majumder, M.; Orain, J. C.; Senyshyn, A.; Prinz-Zwick, M.; Bachus, S.; Tokiwa, Y.; Bert, F.; Khuntia, P.; Büttgen, N.; Tsirlin, A. A.; Gegenwart, P.

2017-11-01

Using thermodynamic measurements, neutron diffraction, nuclear magnetic resonance, and muon spin relaxation, we establish putative quantum spin-liquid behavior in Ba3InIr2O9 , where unpaired electrons are localized on mixed-valence Ir2O9 dimers with Ir4.5 + ions. Despite the antiferromagnetic Curie-Weiss temperature on the order of 10 K, neither long-range magnetic order nor spin freezing are observed down to at least 20 mK, such that spins are short-range correlated and dynamic over nearly three decades in temperature. Quadratic power-law behavior of both the spin-lattice relaxation rate and specific heat indicates the gapless nature of the ground state. We envisage that this exotic behavior may be related to an unprecedented combination of the triangular and buckled honeycomb geometries of nearest-neighbor exchange couplings in the mixed-valence setting.

An experimental and theoretical study of the valence shell photoelectron spectra of 2-chloropyridine and 3-chloropyridine

Science.gov (United States)

Holland, D. M. P.; Powis, I.; Trofimov, A. B.; Menzies, R. C.; Potts, A. W.; Karlsson, L.; Badsyuk, I. L.; Moskovskaya, T. E.; Gromov, E. V.; Schirmer, J.

2017-10-01

experimental spectra. The theoretical work also highlights the formation of satellite states, due to the breakdown of the single particle model of ionization, in the inner valence region.

P450 reductase and cytochrome b5 interactions with cytochrome P450: Effects on house fly CYP6A1 catalysis

OpenAIRE

Murataliev, Marat B.; Guzov, Victor M.; Walker, F. Ann; Feyereisen, René

2008-01-01

The interactions of protein components of the xenobiotic-metabolizing cytochrome P450 system, CYP6A1, P450 reductase, and cytochrome b5 from the house fly (Musca domestica) have been characterized. CYP6A1 activity is determined by the concentration of the CYP6A1-P450 reductase complex, regardless of which protein is present in excess. Both holo- and apo-b5 stimulated CYP6A1 heptachlor epoxidase and steroid hydroxylase activities and influenced the regioselectivity of testosterone hydroxylatio...

Mixing positive and negative valence: Affective-semantic integration of bivalent words.

Science.gov (United States)

Kuhlmann, Michael; Hofmann, Markus J; Briesemeister, Benny B; Jacobs, Arthur M

2016-08-05

Single words have affective and aesthetic properties that influence their processing. Here we investigated the processing of a special case of word stimuli that are extremely difficult to evaluate, bivalent noun-noun-compounds (NNCs), i.e. novel words that mix a positive and negative noun, e.g. 'Bombensex' (bomb-sex). In a functional magnetic resonance imaging (fMRI) experiment we compared their processing with easier-to-evaluate non-bivalent NNCs in a valence decision task (VDT). Bivalent NNCs produced longer reaction times and elicited greater activation in the left inferior frontal gyrus (LIFG) than non-bivalent words, especially in contrast to words of negative valence. We attribute this effect to a LIFG-grounded process of semantic integration that requires greater effort for processing converse information, supporting the notion of a valence representation based on associations in semantic networks.

Cytochrome c catalyzes the in vitro synthesis of arachidonoyl glycine

International Nuclear Information System (INIS)

McCue, Jeffrey M.; Driscoll, William J.; Mueller, Gregory P.

2008-01-01

Long chain fatty acyl glycines are an emerging class of biologically active molecules that occur naturally and produce a wide array of physiological effects. Their biosynthetic pathway, however, remains unknown. Here we report that cytochrome c catalyzes the synthesis of N-arachidonoyl glycine (NAGly) from arachidonoyl coenzyme A and glycine in the presence of hydrogen peroxide. The identity of the NAGly product was verified by isotope labeling and mass analysis. Other heme-containing proteins, hemoglobin and myoglobin, were considerably less effective in generating arachidonoyl glycine as compared to cytochrome c. The reaction catalyzed by cytochrome c in vitro points to its potential role in the formation of NAGly and other long chain fatty acyl glycines in vivo

Approach and Withdrawal Tendencies during Written Word Processing: Effects of Task, Emotional Valence, and Emotional Arousal.

Science.gov (United States)

Citron, Francesca M M; Abugaber, David; Herbert, Cornelia

2015-01-01

The affective dimensions of emotional valence and emotional arousal affect processing of verbal and pictorial stimuli. Traditional emotional theories assume a linear relationship between these dimensions, with valence determining the direction of a behavior (approach vs. withdrawal) and arousal its intensity or strength. In contrast, according to the valence-arousal conflict theory, both dimensions are interactively related: positive valence and low arousal (PL) are associated with an implicit tendency to approach a stimulus, whereas negative valence and high arousal (NH) are associated with withdrawal. Hence, positive, high-arousal (PH) and negative, low-arousal (NL) stimuli elicit conflicting action tendencies. By extending previous research that used several tasks and methods, the present study investigated whether and how emotional valence and arousal affect subjective approach vs. withdrawal tendencies toward emotional words during two novel tasks. In Study 1, participants had to decide whether they would approach or withdraw from concepts expressed by written words. In Studies 2 and 3 participants had to respond to each word by pressing one of two keys labeled with an arrow pointing upward or downward. Across experiments, positive and negative words, high or low in arousal, were presented. In Study 1 (explicit task), in line with the valence-arousal conflict theory, PH and NL words were responded to more slowly than PL and NH words. In addition, participants decided to approach positive words more often than negative words. In Studies 2 and 3, participants responded faster to positive than negative words, irrespective of their level of arousal. Furthermore, positive words were significantly more often associated with "up" responses than negative words, thus supporting the existence of implicit associations between stimulus valence and response coding (positive is up and negative is down). Hence, in contexts in which participants' spontaneous responses are

Pressure and irradiation effects on transport properties of samarium compounds with instable valence

International Nuclear Information System (INIS)

Morillo, J.

1981-01-01

Electron transport properties in samarium compounds with instable valence are studied in this thesis: from SmS in its integer valence phases at common pressure to SmB 6 compound IV at common pressure through SmSsub(1-x)Psub(x) (x 6 is presented [fr

Molecular invariants: atomic group valence

International Nuclear Information System (INIS)

Mundim, K.C.; Giambiagi, M.; Giambiagi, M.S. de.

1988-01-01

Molecular invariants may be deduced in a very compact way through Grassman algebra. In this work, a generalized valence is defined for an atomic group; it reduces to the Known expressions for the case of an atom in a molecule. It is the same of the correlations between the fluctions of the atomic charges qc and qd (C belongs to the group and D does not) around their average values. Numerical results agree with chemical expectation. (author) [pt

Social Annotation Valence: The Impact on Online Informed Consent Beliefs and Behavior.

Science.gov (United States)

Balestra, Martina; Shaer, Orit; Okerlund, Johanna; Westendorf, Lauren; Ball, Madeleine; Nov, Oded

2016-07-20

Social media, mobile and wearable technology, and connected devices have significantly expanded the opportunities for conducting biomedical research online. Electronic consent to collecting such data, however, poses new challenges when contrasted to traditional consent processes. It reduces the participant-researcher dialogue but provides an opportunity for the consent deliberation process to move from solitary to social settings. In this research, we propose that social annotations, embedded in the consent form, can help prospective participants deliberate on the research and the organization behind it in ways that traditional consent forms cannot. Furthermore, we examine the role of the comments' valence on prospective participants' beliefs and behavior. This study focuses specifically on the influence of annotations' valence on participants' perceptions and behaviors surrounding online consent for biomedical research. We hope to shed light on how social annotation can be incorporated into digitally mediated consent forms responsibly and effectively. In this controlled between-subjects experiment, participants were presented with an online consent form for a personal genomics study that contained social annotations embedded in its margins. Individuals were randomly assigned to view the consent form with positive-, negative-, or mixed-valence comments beside the text of the consent form. We compared participants' perceptions of being informed and having understood the material, their trust in the organization seeking the consent, and their actual consent across conditions. We find that comment valence has a marginally significant main effect on participants' perception of being informed (F2=2.40, P=.07); specifically, participants in the positive condition (mean 4.17, SD 0.94) felt less informed than those in the mixed condition (mean 4.50, SD 0.69, P=.09). Comment valence also had a marginal main effect on the extent to which participants reported trusting the

Low-temperature kinetic measurements of microsecond freeze-hyperquench (MHQ) cytochrome oxidase monitored by UV-visible spectroscopy with a newly designed cuvette.

Science.gov (United States)

Wiertz, F G M; de Vries, S

2006-02-01

A special cuvette was designed to measure optical changes of MHQ (microsecond freeze-hyperquench) powder samples at temperatures below approx. 250 K. Reduced cytochrome c oxidase from Paracoccus denitrificans was reacted with O(2) for 100 micros, frozen as a powder and transferred to the cuvette. Subsequently, cytochrome oxidase was allowed to react further following stepwise increments of the temperature from 100 K up to 250 K while recording spectra between 300 and 700 nm. The temperature was raised only when no further changes in the spectra could be detected. The experiment yielded spectra of the A, P(M), F and O intermediate states. This demonstrated that the catalytic cycle of cytochrome oxidase at low temperature is similar to that at room temperature and so verifies the suitability of this method for the study of enzymes with high catalytic-centre activity.

Verbal instructions targeting valence alter negative conditional stimulus evaluations (but do not affect reinstatement rates).

Science.gov (United States)

Luck, Camilla C; Lipp, Ottmar V

2018-02-01

Negative conditional stimulus (CS) valence acquired during fear conditioning may enhance fear relapse and is difficult to remove as it extinguishes slowly and does not respond to the instruction that unconditional stimulus (US) presentations will cease. We examined whether instructions targeting CS valence would be more effective. In Experiment 1, an image of one person (CS+) was paired with an aversive US, while another (CS-) was presented alone. After acquisition, participants were given positive information about the CS+ poser and negative information about the CS- poser. Instructions reversed the pattern of differential CS valence present during acquisition and eliminated differential electrodermal responding. In Experiment 2, we compared positive and negative CS revaluation by providing positive/negative information about the CS+ and neutral information about CS-. After positive revaluation, differential valence was removed and differential electrodermal responding remained intact. After negative revaluation, differential valence was strengthened and differential electrodermal responding was eliminated. Unexpectedly, the instructions did not affect the reinstatement of differential electrodermal responding.

The uranium valence in the Cs-U-O system: crystal structures and thin layers contribution to the physico-chemical study of grain boundaries in irradiated fuel

International Nuclear Information System (INIS)

Van Den Berghe, S.

2002-01-01

The document is an abstract of a PhD thesis. The PhD thesis investigates the way in which cesium, through its effect on oxygen, modifies the uranium environment and in consequence the valence state of the uranium atom itself. To this end, the crystallographic structure and local uranium environment of several uranium uranates has been determined by Rietveld refinement of neutron and X-ray diffraction data. Thin layers of stoichiometric uranium dioxide were prepared using sputter deposition techniques and used to model interactions on the grain boundaries. They were covered with cesium and exposed to controlled amounts of oxygen, while the uranium valence state was monitored with Ultraviolet Photoelectron Spectroscopy and XPS

Increasing Protein Charge State When Using Laser Electrospray Mass Spectrometry

Science.gov (United States)

Karki, Santosh; Flanigan, Paul M.; Perez, Johnny J.; Archer, Jieutonne J.; Levis, Robert J.

2015-05-01

Femtosecond (fs) laser vaporization is used to transfer cytochrome c, myoglobin, lysozyme, and ubiquitin from the condensed phase into an electrospray (ES) plume consisting of a mixture of a supercharging reagent, m-nitrobenzyl alcohol ( m-NBA), and trifluoroacetic acid (TFA), acetic acid (AA), or formic acid (FA). Interaction of acid-sensitive proteins like cytochrome c and myoglobin with the highly charged ES droplets resulted in a shift to higher charge states in comparison with acid-stable proteins like lysozyme and ubiquitin. Laser electrospray mass spectrometry (LEMS) measurements showed an increase in both the average charge states (Zavg) and the charge state with maximum intensity (Zmode) for acid-sensitive proteins compared with conventional electrospray ionization mass spectrometry (ESI-MS) under equivalent solvent conditions. A marked increase in ion abundance of higher charge states was observed for LEMS in comparison with conventional electrospray for cytochrome c (ranging from 19+ to 21+ versus 13+ to 16+) and myoglobin (ranging from 19+ to 26+ versus 18+ to 21+) using an ES solution containing m-NBA and TFA. LEMS measurements as a function of electrospray flow rate yielded increasing charge states with decreasing flow rates for cytochrome c and myoglobin.

NADPH–Cytochrome P450 Oxidoreductase: Roles in Physiology, Pharmacology, and Toxicology

Science.gov (United States)

Ding, Xinxin; Wolf, C. Roland; Porter, Todd D.; Pandey, Amit V.; Zhang, Qing-Yu; Gu, Jun; Finn, Robert D.; Ronseaux, Sebastien; McLaughlin, Lesley A.; Henderson, Colin J.; Zou, Ling; Flück, Christa E.

2013-01-01

This is a report on a symposium sponsored by the American Society for Pharmacology and Experimental Therapeutics and held at the Experimental Biology 2012 meeting in San Diego, California, on April 25, 2012. The symposium speakers summarized and critically evaluated our current understanding of the physiologic, pharmacological, and toxicological roles of NADPH–cytochrome P450 oxidoreductase (POR), a flavoprotein involved in electron transfer to microsomal cytochromes P450 (P450), cytochrome b5, squalene mono-oxygenase, and heme oxygenase. Considerable insight has been derived from the development and characterization of mouse models with conditional Por deletion in particular tissues or partial suppression of POR expression in all tissues. Additional mouse models with global or conditional hepatic deletion of cytochrome b5 are helping to clarify the P450 isoform- and substrate-specific influences of cytochrome b5 on P450 electron transfer and catalytic function. This symposium also considered studies using siRNA to suppress POR expression in a hepatoma cell–culture model to explore the basis of the hepatic lipidosis phenotype observed in mice with conditional deletion of Por in liver. The symposium concluded with a strong translational perspective, relating the basic science of human POR structure and function to the impacts of POR genetic variation on human drug and steroid metabolism. PMID:23086197

Acrolein, A Reactive Product of Lipid Peroxidation, Induces Oxidative Modification of Cytochrome c

Energy Technology Data Exchange (ETDEWEB)

Kang, Jung Hoon [Cheongju Univ., Cheongju (Korea, Republic of)

2013-11-15

Acrolein (ACR) is a well-known carbonyl toxin produced by lipid peroxidation of polyunsaturated fatty acids, which is involved in the pathogenesis of neurodegenerative disorders such as Alzheimer's disease (AD). In Alzheimer's brain, ACR was found to be elevated in hippocampus and temporal cortex where oxidative stress is high. In this study, we evaluated oxidative modification of cytochrome c occurring after incubation with ACR. When cytochrome c was incubated with ACR, protein aggregation increased in a dose-dependent manner. The formation of carbonyl compounds and the release of iron were obtained in ACR-treated cytochrome c. Reactive oxygen species scavengers and iron specific chelator inhibited the ACR-mediated cytochrome c modification and carbonyl compound formation. Our data demonstrate that oxidative damage of cytochrome c by ACR might induce disruption of cyotochrome c structure and iron mishandling as a contributing factor to the pathology of AD.

Acrolein, A Reactive Product of Lipid Peroxidation, Induces Oxidative Modification of Cytochrome c

International Nuclear Information System (INIS)

Kang, Jung Hoon

2013-01-01

Acrolein (ACR) is a well-known carbonyl toxin produced by lipid peroxidation of polyunsaturated fatty acids, which is involved in the pathogenesis of neurodegenerative disorders such as Alzheimer's disease (AD). In Alzheimer's brain, ACR was found to be elevated in hippocampus and temporal cortex where oxidative stress is high. In this study, we evaluated oxidative modification of cytochrome c occurring after incubation with ACR. When cytochrome c was incubated with ACR, protein aggregation increased in a dose-dependent manner. The formation of carbonyl compounds and the release of iron were obtained in ACR-treated cytochrome c. Reactive oxygen species scavengers and iron specific chelator inhibited the ACR-mediated cytochrome c modification and carbonyl compound formation. Our data demonstrate that oxidative damage of cytochrome c by ACR might induce disruption of cyotochrome c structure and iron mishandling as a contributing factor to the pathology of AD

Dissociable modulation of overt visual attention in valence and arousal revealed by topology of scan path.

Directory of Open Access Journals (Sweden)

Jianguang Ni

Full Text Available Emotional stimuli have evolutionary significance for the survival of organisms; therefore, they are attention-grabbing and are processed preferentially. The neural underpinnings of two principle emotional dimensions in affective space, valence (degree of pleasantness and arousal (intensity of evoked emotion, have been shown to be dissociable in the olfactory, gustatory and memory systems. However, the separable roles of valence and arousal in scene perception are poorly understood. In this study, we asked how these two emotional dimensions modulate overt visual attention. Twenty-two healthy volunteers freely viewed images from the International Affective Picture System (IAPS that were graded for affective levels of valence and arousal (high, medium, and low. Subjects' heads were immobilized and eye movements were recorded by camera to track overt shifts of visual attention. Algebraic graph-based approaches were introduced to model scan paths as weighted undirected path graphs, generating global topology metrics that characterize the algebraic connectivity of scan paths. Our data suggest that human subjects show different scanning patterns to stimuli with different affective ratings. Valence salient stimuli (with neutral arousal elicited faster and larger shifts of attention, while arousal salient stimuli (with neutral valence elicited local scanning, dense attention allocation and deep processing. Furthermore, our model revealed that the modulatory effect of valence was linearly related to the valence level, whereas the relation between the modulatory effect and the level of arousal was nonlinear. Hence, visual attention seems to be modulated by mechanisms that are separate for valence and arousal.

Resonant photoemission at core-level shake-up thresholds: Valence-band satellites in nickel

International Nuclear Information System (INIS)

Bjoerneholm, O.; Andersen, J.N.; Wigren, C.; Nilsson, A.; Nyholm, R.; Ma; Ortensson, N.

1990-01-01

Three-hole satellites (3d 7 final-state configuration) in the nickel valence-band photoelectron spectrum have been identified at 13 and 18 eV binding energy with use of synchrotron radiation from the MAX storage ring. The three-hole satellites show resonances at photon energies close to the threshold for excitation of 3p 5 3d 9 core-hole shake-up states. The 13-eV satellite also shows a resonance directly at the 3p threshold. This is interpreted as an interference between the direct three-hole ionization and a shake-up transition in the Auger decay of the 3p hole. This shake-up process is also identified directly in the M 2,3 M 4,5 M 4,5 Auger spectrum

Redox reactions of cytochrome c in isolated mitochondria exposed to blue or red lasers using resonance Raman spectroscopy

Science.gov (United States)

Denton, Michael L.; Gonzalez, Cherry C.; Noojin, Gary D.; Yakovlev, Vladislav V.

2018-02-01

Resonance Raman spectroscopy of cytochrome c was used to follow reduction/oxidation (redox) states of isolated mitochondria in response to blue or red laser exposure. Mitochondria were isolated from hTERT-RPE1 cells and were kept in a buffer formulation known to be conducive to electron transport chain (ETC) activity. Using either pyruvate or succinate as substrates for ETC, we found differences in the redox responses of cytochrome c for different exposure laser irradiance and excitation wavelength. We anticipate that the proposed new method will be valuable in the study of metabolic processes in mitochondria in response to low level laser exposure, and thus aid in elucidating the mechanism(s) of photobiomodulation.

A study on the interaction of horse heart cytochrome c with some conventional and ionic liquid surfactants probed by ultraviolet-visible and fluorescence spectroscopic techniques.

Science.gov (United States)

Mondal, Satyajit; Das, Bijan

2018-06-05

The interactions of a protein cytochrome c with some selected conventional and ionic liquid surfactants have been investigated at pH7.4 using ultraviolet-visible and fluorescence spectroscopic techniques. We used four conventional surfactants - cetyltrimethylammonium bromide (CTAB), dodecyltrimethylammonium bromide (DTAB), sodium N-dodecanoylsarcosinate (SDDS), and N-decanoyl-N-methylglucamine (Mega 10), and a surface active ionic liquid 1-hexadecyl-3-methylimidazolium chloride (C 16 MeImCl). All the investigated surfactants were found to induce an unfolding of the protein cytochrome c. In presence of CTAB, SDDS and C 16 MeImCl, the heme iron atom was found to loose methionine from its axial position. Differential binding of the surfactant monomers and their micelles to the protein molecules was inferred. The ionic surfactants were found to be more effective than the nonionic one in unfolding the investigated protein. However, the extent of binding of CTAB/C 16 MeImCl to cytochrome c reaches a plateau past the critical micellization concentration (cmc) of the surfactant. For each of the cytochrome c-DTAB, cytochrome c-SDDS and cytochrome c-Mega 10 system, although there exists an inflection in the surfactant-binding, saturation point could not be detected. It has been demonstrated from the ultraviolet-visible spectral studies that the oxidation state of iron in cytochrome c does not change when the protein binds with the investigated surfactants. Copyright © 2018 Elsevier B.V. All rights reserved.

Chemical labeling studies on isolated and vesicular bovine heart mitochondrial cytochrome c oxidase

International Nuclear Information System (INIS)

Venzke, K.S.; Reynolds, K.A.; Prochaska, L.J.

1987-01-01

Bovine heart cytochrome c oxidase dispersed in Triton X-100, Tween 80, or dodecyl maltoside was reacted with the water-soluble reagents [ 35 S]-diazonium benzene sulfonate (DABS) (10-100 μM) or [ 125 I]-iodo-DABS (34-55 nM) to map the surface topography of the enzyme in different protein aggregation states. Both reagents gave similar labeling profiles of the enzyme under all conditions. Subunits II, III, and VII were extensively labeled by DABS, while subunits I and VI were unreactive with DABS in each detergent. Subunit V exhibited an increase in DABS labeling when the enzyme was reacted in Tween 80 as compared to the enzyme in Triton X-100 or dodecyl maltoside. Also, components b and c showed an increase in DABS reactivity when the enzyme was modified in dodecyl maltoside. In general, the labeling profile of the enzyme in dodecyl maltoside resembled that of the enzyme in Triton X-100, emphasizing that the mechanism of dispersal of the enzyme by both detergents is similar. Cytochrome c oxidase incorporated into phosphatidylglycerol:phosphatidylcholine(1:20)(w:w) phospholipid vesicles (COV) by cholate dialysis was reacted with DABS and subunits II and III were significantly labeled. Approximately 65-70% of the enzyme in COV was oriented with the cytochrome c binding domain facing the extravesicular medium, as determined by comparison of the DABS labeling in subunit IV in detergent-lysed and intact COV

Event-related brain potential correlates of words' emotional valence irrespective of arousal and type of task.

Science.gov (United States)

Espuny, Javier; Jiménez-Ortega, Laura; Casado, Pilar; Fondevila, Sabela; Muñoz, Francisco; Hernández-Gutiérrez, David; Martín-Loeches, Manuel

2018-03-23

Many Event-Related brain Potential (ERP) experiments have explored how the two main dimensions of emotion, arousal and valence, affect linguistic processing. However, the heterogeneity of experimental paradigms and materials has led to mixed results. In the present study, we aim to clarify words' emotional valence effects on ERP when arousal is controlled, and determine whether these effects may vary as a function of the type of task performed. For these purposes, we designed an ERP experiment with the valence of words manipulated, and arousal equated across valences. The participants performed two types of task: in one, they had to read aloud each word, written in black on a white background; in the other, they had to name the color of the ink in which each word was written. The results showed the main effects of valence irrespective of task, and no interaction between valence and task. The most marked effects of valence were in response to negative words, which elicited an Early Posterior Negativity (EPN) and a Late Positive Complex (LPC). Our results suggest that, when arousal is controlled, the cognitive information in negative words triggers a 'negativity bias', these being the only words able to elicit emotion-related ERP modulations. Moreover, these modulations are largely unaffected by the types of task explored here. Copyright © 2018 Elsevier B.V. All rights reserved.

Can the second order multireference perturbation theory be considered a reliable tool to study mixed-valence compounds?

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Pastore, Mariachiara; Helal, Wissam; Evangelisti, Stefano; Leininger, Thierry; Malrieu, Jean-Paul; Maynau, Daniel; Angeli, Celestino; Cimiraglia, Renzo

2008-05-07

In this paper, the problem of the calculation of the electronic structure of mixed-valence compounds is addressed in the frame of multireference perturbation theory (MRPT). Using a simple mixed-valence compound (the 5,5(') (4H,4H('))-spirobi[ciclopenta[c]pyrrole] 2,2('),6,6(') tetrahydro cation), and the n-electron valence state perturbation theory (NEVPT2) and CASPT2 approaches, it is shown that the ground state (GS) energy curve presents an unphysical "well" for nuclear coordinates close to the symmetric case, where a maximum is expected. For NEVPT, the correct shape of the energy curve is retrieved by applying the MPRT at the (computationally expensive) third order. This behavior is rationalized using a simple model (the ionized GS of two weakly interacting identical systems, each neutral system being described by two electrons in two orbitals), showing that the unphysical well is due to the canonical orbital energies which at the symmetric (delocalized) conformation lead to a sudden modification of the denominators in the perturbation expansion. In this model, the bias introduced in the second order correction to the energy is almost entirely removed going to the third order. With the results of the model in mind, one can predict that all MRPT methods in which the zero order Hamiltonian is based on canonical orbital energies are prone to present unreasonable energy profiles close to the symmetric situation. However, the model allows a strategy to be devised which can give a correct behavior even at the second order, by simply averaging the orbital energies of the two charge-localized electronic states. Such a strategy is adopted in a NEVPT2 scheme obtaining a good agreement with the third order results based on the canonical orbital energies. The answer to the question reported in the title (is this theoretical approach a reliable tool for a correct description of these systems?) is therefore positive, but care must be exercised, either in defining the orbital

Valence and inner-valence shell dissociative photoionization of CO in the 26-33 eV range. II. Molecular-frame and recoil-frame photoelectron angular distributions

DEFF Research Database (Denmark)

Lebech, M.; Houver, J.C.; Raseev, G.

2012-01-01

Experimental and theoretical results for molecular-frame photoemission are presented for inner-valence shell photoionization of the CO molecule induced by linearly and circularly polarized light. The experimental recoil frame photoelectron angular distributions (RFPADs) obtained from dissociative...... photoionization measurements where the velocities of the ionic fragment and photoelectron were detected in coincidence, are compared to RFPADs computed using the multichannel Schwinger configuration interaction method. The formalism for including a finite lifetime of the predissociative ion state is presented...... for the case of general elliptically polarized light, to obtain the RFPAD rather than the molecular frame photoelectron angular distribution (MFPAD), which would be obtained with the assumption of instantaneous dissociation. We have considered photoionization of CO for the photon energies of 26.0 eV, 29.5 e...

Lattice QCD with mixed action - Borici-Creutz valence quark on staggered sea

Science.gov (United States)

Basak, Subhasish; Goswami, Jishnu; Chakrabarti, Dipankar

2018-03-01

Mixed action lattice QCD with Borici-Creutz valence quarks on staggered sea is investigated. The counter terms in Borici-Creutz action are fixed nonperturbatively to restore the broken symmetries. On symmetry restoration, the usual signatures of partial quenching / unitarity violation like negative scalar correlator are observed. The size of unitarity violation due to different discretization of valence and sea quark is determined by measuring Δmix.

Reply to Isgur's comments on valence QCD

International Nuclear Information System (INIS)

Liu, K.F.

2000-01-01

With the goal of understanding the complexity of QCD and the role of symmetry in dynamics, the authors studied a field theory called Valence QCD (VQCD) in which the Z graphs are forbidden so that the Fock space is limited to the valence quarks. The authors calculated nucleon form factors, matrix elements, and hadron masses both with this theory and with quenched QCD on a set of lattices with the same gauge background. Comparing the results of the lattice calculations in these two theories, the authors drew conclusions regarding the SU(6) valence quark model and chiral symmetry. While recognizing the goal of VQCD, Nathan Isgur disagrees on some of the conclusions the authors have drawn. The foremost objection raised in section 2 is to their suggestion that the major part of the hyperfine splittings in baryons is due to Goldstone boson exchange and not one-gluon-exchange (OGE) interactions. The logic of Isgur's objection is that VQCD yields a spectroscopy vastly different from quenched QCD and therefore the structure of the hadrons (to which hyperfine splittings in a quark model are intimately tied) is also suspect so no definite conclusions are possible. To put this into perspective it should be emphasized at the outset that spectroscopy is only one aspect of hadron physics examined in section 1. The authors have studied the axial and scalar couplings of nucleon in terms of F A /D A and F S /D S , the neutron to proton magnetic moment ratio μn/μp, and various form factors. None of these results reveal any pathologies of hadron structure and turn out to be close to the SU(6) relations, as expected. In fact this is what motivated the study of valence degrees of freedom via VQCD. In section 2 the authors address specific issues related to spectroscopy in VQCD. Isgur also presented more general arguments against the idea of boson exchange as a contributor to hyperfine effects. A cornerstone of his discussion is the unifying aspect of OGE in a quark model picture. The

Disruption of a hydrogen bond network in human versus spider monkey cytochrome c affects heme crevice stability.

Science.gov (United States)

Goldes, Matthew E; Jeakins-Cooley, Margaret E; McClelland, Levi J; Mou, Tung-Chung; Bowler, Bruce E

2016-05-01

The hypothesis that the recent rapid evolution of primate cytochromes c, which primarily involves residues in the least stable Ω-loop (Ω-loop C, residues 40-57), stabilizes the heme crevice of cytochrome c relative to other mammals, is tested. To accomplish this goal, we have compared the properties of human and spider monkey cytochrome c and a set of four variants produced in the process of converting human cytochrome c into spider monkey cytochrome c. The global stability of all variants has been measured by guanidine hydrochloride denaturation. The stability of the heme crevice has been assessed with the alkaline conformational transition. Structural insight into the effects of the five amino acid substitutions needed to convert human cytochrome c into spider monkey cytochrome c is provided by a 1.15Å resolution structure of spider monkey cytochrome c. The global stability for all variants is near 9.0kcal/mol at 25°C and pH7, which is higher than that observed for other mammalian cytochromes c. The heme crevice stability is more sensitive to the substitutions required to produce spider monkey cytochrome c with decreases of up to 0.5 units in the apparent pKa of the alkaline conformational transition relative to human cytochrome c. The structure of spider monkey cytochrome c indicates that the Y46F substitution destabilizes the heme crevice by disrupting an extensive hydrogen bond network that connects three surface loops including Ω-loop D (residues 70-85), which contains the Met80 heme ligand. Copyright © 2015 Elsevier Inc. All rights reserved.

Size-dependent valence change in small Pr, Nd, and Sm clusters isolated in solid Ar

International Nuclear Information System (INIS)

Luebcke, M.; Sonntag, B.; Niemann, W.; Rabe, P.

1986-01-01

The L/sub III/ absorption thresholds of Pr, Nd, and Sm clusters isolated in solid Ar are marked by prominent white lines. The lines ascribed to divalent and trivalent rare-earth metals are well separated in energy. From the relative intensities of these lines an average valence of the rare-earth atoms in the cluster has been determined. For dimers and trimers the average valence is close to 2, the value for free atoms. For clusters consisting of more than 20 atoms the average valence approaches 3, the value for bulk metals. In between the valence changes abruptly, indicating the existence of a critical cluster size of approximately 5 atoms for Pr and Nd and of 13 atoms for Sm

Electronic and transport properties of Cobalt-based valence tautomeric molecules and polymers

Science.gov (United States)

Chen, Yifeng; Calzolari, Arrigo; Buongiorno Nardelli, Marco

2011-03-01

The advancement of molecular spintronics requires further understandings of the fundamental electronic structures and transport properties of prototypical spintronics molecules and polymers. Here we present a density functional based theoretical study of the electronic structures of Cobalt-based valence tautomeric molecules Co III (SQ)(Cat)L Co II (SQ)2 L and their polymers, where SQ refers to the semiquinone ligand, and Cat the catecholate ligand, while L is a redox innocent backbone ligand. The conversion from low-spin Co III ground state to high-spin Co II excited state is realized by imposing an on-site potential U on the Co atom and elongating the Co-N bond. Transport properties are subsequently calculated by extracting electronic Wannier functions from these systems and computing the charge transport in the ballistic regime using a Non-Equilibrium Green's Function (NEGF) approach. Our transport results show distinct charge transport properties between low-spin ground state and high-spin excited state, hence suggesting potential spintronics devices from these molecules and polymers such as spin valves.

Approach and withdrawal tendencies during written word processing: effects of task, emotional valence and emotional arousal

Directory of Open Access Journals (Sweden)

Francesca M. M. Citron

2016-01-01

Full Text Available The affective dimensions of emotional valence and emotional arousal affect processing of verbal and pictorial stimuli. Traditional emotional theories assume a linear relationship between these dimensions, with valence determining the direction of a behaviour (approach vs. withdrawal and arousal its intensity or strength. In contrast, according to the valence-arousal conflict theory, both dimensions are interactively related: positive valence and low arousal (PL are associated with an implicit tendency to approach a stimulus, whereas negative valence and high arousal (NH are associated with withdrawal. Hence, positive, high-arousal (PH and negative, low-arousal (NL stimuli elicit conflicting action tendencies. By extending previous research that used several tasks and methods, the present study investigated whether and how emotional valence and arousal affect subjective approach vs. withdrawal tendencies towards emotional words during two novel tasks. In Study 1, participants had to decide whether they would approach or withdraw from concepts expressed by written words. In Studies 2 and 3 participants had to respond to each word by pressing one of two keys labelled with an arrow pointing upward or downward. Across experiments, positive and negative words, high or low in arousal, were presented. In Study 1 (explicit task, in line with the valence-arousal conflict theory, PH and NL words were responded to more slowly than PL and NH words. In addition, participants decided to approach positive words more often than negative words. In Studies 2 and 3, participants responded faster to positive than negative words, irrespective of their level of arousal. Furthermore, positive words were significantly more often associated with up responses than negative words, thus supporting the existence of implicit associations between stimulus valence and response coding (positive is up and negative is down. Hence, in contexts in which participants’ spontaneous

Time-resolved imaging of purely valence-electron dynamics during a chemical reaction

DEFF Research Database (Denmark)

Hockett, Paul; Bisgaard, Christer Z.; Clarkin, Owen J.

2011-01-01

Chemical reactions are manifestations of the dynamics of molecular valence electrons and their couplings to atomic motions. Emerging methods in attosecond science can probe purely electronic dynamics in atomic and molecular systems(1-6). By contrast, time-resolved structural-dynamics methods...... such as electron(7-10) or X-ray diffraction(11) and X-ray absorption(12) yield complementary information about the atomic motions. Time-resolved methods that are directly sensitive to both valence-electron dynamics and atomic motions include photoelectron spectroscopy(13-15) and high-harmonic generation(16......,17): in both cases, this sensitivity derives from the ionization-matrix element(18,19). Here we demonstrate a time-resolved molecular-frame photoelectron-angular-distribution (TRMFPAD) method for imaging the purely valence-electron dynamics during a chemical reaction. Specifically, the TRMFPADs measured during...

fK /f{pi} in Full QCD with Domain Wall Valence Quarks

Energy Technology Data Exchange (ETDEWEB)

Silas Beane; Paulo Bedaque; Konstantinos Orginos; Martin Savage

2007-05-01

We compute the ratio of pseudoscalar decay constants f{sub K}/f{sub {pi}} using domain-wall valence quarks and rooted improved Kogut-Susskind sea quarks. By employing continuum chiral perturbation theory, we extract the Gasser-Leutwyler low-energy constant L{sub 5}, and extrapolate f{sub K}/f{sub {pi}} to the physical point. We find: f{sub K}/f{sub {pi}} = 1.218 {+-} 0.002{sub -0.024}{sup +0.011} where the first error is statistical and the second error is an estimate of the systematic due to chiral extrapolation and fitting procedures. This value agrees within the uncertainties with the determination by the MILC collaboration, calculated using Kogut-Susskind valence quarks, indicating that systematic errors arising from the choice of lattice valence quark are small.

The use of symmetrized valence and relative motion coordinates for crystal potentials

DEFF Research Database (Denmark)

McMurry, H. L.; Hansen, Flemming Yssing

1980-01-01

Symmetrized valence coordinates are linear combinations of conventional valence coordinates which display the symmetry of a set of atoms bound by the valence bonds. Relative motion coordinates are relative translations, or relative rotations, of two or more strongly bonded groups of atoms among...... which relatively weak forces act. They are useful for expressing interactions between molecules in molecular crystals and should be chosen, also, to reflect the symmetry of the interacting groups. Since coordinates defined by these procedures possess elements of symmetry in common with the bonding...... interaction constants coupling coordinates of unlike symmetry with regard to the crystal point group are necessarily zero. They may be small, also, for coordinates which belong to different representations of the local symmetry when this is not the same as for the crystal. Procedures are given for defining...

Multi-heme Cytochromes in Shewanella oneidensis MR-1: Structures, functions and opportunities

Energy Technology Data Exchange (ETDEWEB)

Breuer, Marian; Rosso, Kevin M.; Blumberger, Jochen; Butt, Julea N.

2014-11-05

Multi-heme cytochromes are employed by a range of microorganisms to transport electrons over distances of up to tens of nanometers. Perhaps the most spectacular utilization of these proteins is in the reduction of extracellular solid substrates, including electrodes and insoluble mineral oxides of Fe(III) and Mn(III/IV), by species of Shewanella and Geobacter. However, multi-heme cytochromes are found in numerous and phylogenetically diverse prokaryotes where they participate in electron transfer and redox catalysis that contributes to biogeochemical cycling of N, S and Fe on the global scale. These properties of multi-heme cytochromes have attracted much interest and contributed to advances in bioenergy applications and bioremediation of contaminated soils. Looking forward there are opportunities to engage multi-heme cytochromes for biological photovoltaic cells, microbial electrosynthesis and developing bespoke molecular devices. As a consequence it is timely to review our present understanding of these proteins and we do this here with a focus on the multitude of functionally diverse multi-heme cytochromes in Shewanella oneidensis MR-1. We draw on findings from experimental and computational approaches which ideally complement each other in the study of these systems: computational methods can interpret experimentally determined properties in terms of molecular structure to cast light on the relation between structure and function. We show how this synergy has contributed to our understanding of multi-heme cytochromes and can be expected to continue to do so for greater insight into natural processes and their informed exploitation in biotechnologies.

Multiple-output support vector machine regression with feature selection for arousal/valence space emotion assessment.

Science.gov (United States)

Torres-Valencia, Cristian A; Álvarez, Mauricio A; Orozco-Gutiérrez, Alvaro A

2014-01-01

Human emotion recognition (HER) allows the assessment of an affective state of a subject. Until recently, such emotional states were described in terms of discrete emotions, like happiness or contempt. In order to cover a high range of emotions, researchers in the field have introduced different dimensional spaces for emotion description that allow the characterization of affective states in terms of several variables or dimensions that measure distinct aspects of the emotion. One of the most common of such dimensional spaces is the bidimensional Arousal/Valence space. To the best of our knowledge, all HER systems so far have modelled independently, the dimensions in these dimensional spaces. In this paper, we study the effect of modelling the output dimensions simultaneously and show experimentally the advantages in modeling them in this way. We consider a multimodal approach by including features from the Electroencephalogram and a few physiological signals. For modelling the multiple outputs, we employ a multiple output regressor based on support vector machines. We also include an stage of feature selection that is developed within an embedded approach known as Recursive Feature Elimination (RFE), proposed initially for SVM. The results show that several features can be eliminated using the multiple output support vector regressor with RFE without affecting the performance of the regressor. From the analysis of the features selected in smaller subsets via RFE, it can be observed that the signals that are more informative into the arousal and valence space discrimination are the EEG, Electrooculogram/Electromiogram (EOG/EMG) and the Galvanic Skin Response (GSR).

The influence of valence and arousal on reasoning: Affective priming in the semantic verification task

Directory of Open Access Journals (Sweden)

Orlić Ana

2014-01-01

Full Text Available The aim of the present study was to examine the effects of affective valence and arousal on the reasoning process. Reasoning was measured using a semantic verification task and the influence of valence and arousal was tracked using the affective priming paradigm. Primes were photographs varied on two dimensions - emotional valence (positive, neutral, negative and arousal (high, low. Forty-nine psychology students participated in the experiment. Results showed that reaction time needed for semantic verification was significantly faster for positive-high arousing in comparison to positive-low arousing condition and for neutral high arousing in comparison to neutral-low arousing condition, but there were no significant differences in negative low and high arousing conditions. Also, significant differences were found among all three valences in high arousing conditions and there were no such differences in low arousing conditions. These results reveal the importance of both arousal and valence in the research on the influence of emotions on the reasoning process. [Projekat Ministarstva nauke Republike Srbije, br. 179033

Immobilized unfolded cytochrome c acts as a catalyst for dioxygen reduction.

Science.gov (United States)

Tavagnacco, Claudio; Monari, Stefano; Ranieri, Antonio; Bortolotti, Carlo Augusto; Peressini, Silvia; Borsari, Marco

2011-10-21

Unfolding turns immobilized cytochrome c into a His-His ligated form endowed with catalytic activity towards O(2), which is absent in the native protein. Dioxygen could be used by naturally occurring unfolded cytochrome c as a substrate for the production of partially reduced oxygen species (PROS) contributing to the cell oxidative stress.

Interpersonal Valence Dimensions as Discriminators of Communication Contexts: An Empirical Assessment of Dyadic Linkages.

Science.gov (United States)

Garrison, John P.; And Others

The capability of 14 interpersonal dimensions to predict dyadic communication contexts was investigated in this study. Friend, acquaintance, co-worker, and family contexts were examined. The interpersonal valence construct, based on a coactive or mutual-causal paradigm, encompasses traditional source-valence components (credibility, power,…

Valence quark annihilation and the total charge in the forward hemisphere of hadron-hadron reactions

International Nuclear Information System (INIS)

Szczekowski, M.

1980-01-01

The consequences of the valence quark annihilation (VQA) mechanism on the energy behaviour of the total net charge for final state particles in the forward c.m.s. hemisphere (Qsub(F)) in K +- p, π + p and pp reactions is examined. The data are in qualitative agreement with VQA model predictions and suggest that at low energies (psub(LAB) approximately 10 GeV/c) the VQA provides the dominating contribution to Qsub(F) in K - p and π +- p interactions. (author)

The Relation Between Valence and Arousal in Subjective Experience Varies With Personality and Culture.

Science.gov (United States)

Kuppens, Peter; Tuerlinckx, Francis; Yik, Michelle; Koval, Peter; Coosemans, Joachim; Zeng, Kevin J; Russell, James A

2017-08-01

While in general arousal increases with positive or negative valence (a so-called V-shaped relation), there are large differences among individuals in how these two fundamental dimensions of affect are related in people's experience. In two studies, we examined two possible sources of this variation: personality and culture. In Study 1, participants (Belgian university students) recalled a recent event that was characterized by high or low valence or arousal and reported on their feelings and their personality in terms of the Five-Factor Model. In Study 2, participants from Canada, China/Hong Kong, Japan, Korea, and Spain reported on their feelings in a thin slice of time and on their personality. In Study 1, we replicated the V-shape as characterizing the relation between valence and arousal, and identified personality correlates of experiencing particular valence-arousal combinations. In Study 2, we documented how the V-shaped relation varied as a function of Western versus Eastern cultural background and personality. The results showed that the steepness of the V-shaped relation between valence and arousal increases with Extraversion within cultures, and with a West-East distinction between cultures. Implications for the personality-emotion link and research on cultural differences in affect are discussed. © 2016 Wiley Periodicals, Inc.

Simultaneous Conduction and Valence Band Quantization in Ultrashallow High-Density Doping Profiles in Semiconductors

Science.gov (United States)

Mazzola, F.; Wells, J. W.; Pakpour-Tabrizi, A. C.; Jackman, R. B.; Thiagarajan, B.; Hofmann, Ph.; Miwa, J. A.

2018-01-01

We demonstrate simultaneous quantization of conduction band (CB) and valence band (VB) states in silicon using ultrashallow, high-density, phosphorus doping profiles (so-called Si:P δ layers). We show that, in addition to the well-known quantization of CB states within the dopant plane, the confinement of VB-derived states between the subsurface P dopant layer and the Si surface gives rise to a simultaneous quantization of VB states in this narrow region. We also show that the VB quantization can be explained using a simple particle-in-a-box model, and that the number and energy separation of the quantized VB states depend on the depth of the P dopant layer beneath the Si surface. Since the quantized CB states do not show a strong dependence on the dopant depth (but rather on the dopant density), it is straightforward to exhibit control over the properties of the quantized CB and VB states independently of each other by choosing the dopant density and depth accordingly, thus offering new possibilities for engineering quantum matter.

Study of valence of cerium and praseodymium ions in Pr1-xCexO2 solid solutions

International Nuclear Information System (INIS)

Gartsman, K.G.; Kartenko, N.F.; Melekh, B.T.

1990-01-01

Effect of preparation conditions of Pr 1-x Ce x O 2 solid solutions on Ce and Pr ion valence within Pr 1-x Ce x O 2 system is studied. The data obtained enable to conclude that praseodymium may depending on annealing conditions change its state from Pr 3+ to Pr 4+ , while Ce 4+ is stable in Pr 1-x Ce x O 2 solid solutions

Music, emotion, and time perception: the influence of subjective emotional valence and arousal?

Science.gov (United States)

Droit-Volet, Sylvie; Ramos, Danilo; Bueno, José L. O.; Bigand, Emmanuel

2013-01-01

The present study used a temporal bisection task with short (2 s) stimulus durations to investigate the effect on time estimation of several musical parameters associated with emotional changes in affective valence and arousal. In order to manipulate the positive and negative valence of music, Experiments 1 and 2 contrasted the effect of musical structure with pieces played normally and backwards, which were judged to be pleasant and unpleasant, respectively. This effect of valence was combined with a subjective arousal effect by changing the tempo of the musical pieces (fast vs. slow) (Experiment 1) or their instrumentation (orchestral vs. piano pieces). The musical pieces were indeed judged more arousing with a fast than with a slow tempo and with an orchestral than with a piano timbre. In Experiment 3, affective valence was also tested by contrasting the effect of tonal (pleasant) vs. atonal (unpleasant) versions of the same musical pieces. The results showed that the effect of tempo in music, associated with a subjective arousal effect, was the major factor that produced time distortions with time being judged longer for fast than for slow tempi. When the tempo was held constant, no significant effect of timbre on the time judgment was found although the orchestral music was judged to be more arousing than the piano music. Nevertheless, emotional valence did modulate the tempo effect on time perception, the pleasant music being judged shorter than the unpleasant music. PMID:23882233

Music, Emotion and Time Perception: The influence of subjective emotional valence and arousal?

Directory of Open Access Journals (Sweden)

SYLVIE eDROIT-VOLET

2013-07-01

Full Text Available The present study used a temporal bisection task with short (< 2 s and long (> 2 s stimulus durations to investigate the effect on time estimation of several musical parameters associated with emotional changes in affective valence and arousal. In order to manipulate the positive and negative valence of music, Experiments 1 and 2 contrasted the effect of musical structure with pieces played normally and backwards, which were judged to be pleasant and unpleasant, respectively. This effect of valence was combined with a subjective arousal effect by changing the tempo of the musical pieces (fast vs. slow (Experiment 1 or their instrumentation (orchestral vs. piano pieces. The musical pieces were indeed judged more arousing with a fast than with a slow tempo and with an orchestral than with a piano timbre. In Experiment 3, affective valence was also tested by contrasting the effect of tonal (pleasant versus atonal (unpleasant versions of the same musical pieces. The results showed that the effect of tempo in music, associated with a subjective arousal effect, was the major factor that produced time distortions with time being judged longer for fast than for slow tempi. When the tempo was held constant, no significant effect of timbre on the time judgment was found although the orchestral music was judged to be more arousing than the piano music. Nevertheless, emotional valence did modulate the tempo effect on time perception, the pleasant music being judged shorter than the unpleasant music.

Music, emotion, and time perception: the influence of subjective emotional valence and arousal?

Science.gov (United States)

Droit-Volet, Sylvie; Ramos, Danilo; Bueno, José L O; Bigand, Emmanuel

2013-01-01

The present study used a temporal bisection task with short (2 s) stimulus durations to investigate the effect on time estimation of several musical parameters associated with emotional changes in affective valence and arousal. In order to manipulate the positive and negative valence of music, Experiments 1 and 2 contrasted the effect of musical structure with pieces played normally and backwards, which were judged to be pleasant and unpleasant, respectively. This effect of valence was combined with a subjective arousal effect by changing the tempo of the musical pieces (fast vs. slow) (Experiment 1) or their instrumentation (orchestral vs. piano pieces). The musical pieces were indeed judged more arousing with a fast than with a slow tempo and with an orchestral than with a piano timbre. In Experiment 3, affective valence was also tested by contrasting the effect of tonal (pleasant) vs. atonal (unpleasant) versions of the same musical pieces. The results showed that the effect of tempo in music, associated with a subjective arousal effect, was the major factor that produced time distortions with time being judged longer for fast than for slow tempi. When the tempo was held constant, no significant effect of timbre on the time judgment was found although the orchestral music was judged to be more arousing than the piano music. Nevertheless, emotional valence did modulate the tempo effect on time perception, the pleasant music being judged shorter than the unpleasant music.

MacA is a second cytochrome c peroxidase of Geobacter sulfurreducens.

Science.gov (United States)

Seidel, Julian; Hoffmann, Maren; Ellis, Katie E; Seidel, Antonia; Spatzal, Thomas; Gerhardt, Stefan; Elliott, Sean J; Einsle, Oliver

2012-04-03

The metal-reducing δ-proteobacterium Geobacter sulfurreducens produces a large number of c-type cytochromes, many of which have been implicated in the transfer of electrons to insoluble metal oxides. Among these, the dihemic MacA was assigned a central role. Here we have produced G. sulfurreducens MacA by recombinant expression in Escherichia coli and have solved its three-dimensional structure in three different oxidation states. Sequence comparisons group MacA into the family of diheme cytochrome c peroxidases, and the protein indeed showed hydrogen peroxide reductase activity with ABTS(-2) as an electron donor. The observed K(M) was 38.5 ± 3.7 μM H(2)O(2) and v(max) was 0.78 ± 0.03 μmol of H(2)O(2)·min(-1)·mg(-1), resulting in a turnover number k(cat) = 0.46 · s(-1). In contrast, no Fe(III) reductase activity was observed. MacA was found to display electrochemical properties similar to other bacterial diheme peroxidases, in addition to the ability to electrochemically mediate electron transfer to the soluble cytochrome PpcA. Differences in activity between CcpA and MacA can be rationalized with structural variations in one of the three loop regions, loop 2, that undergoes conformational changes during reductive activation of the enzyme. This loop is adjacent to the active site heme and forms an open loop structure rather than a more rigid helix as in CcpA. For the activation of the protein, the loop has to displace the distal ligand to the active site heme, H93, in loop 1. A H93G variant showed an unexpected formation of a helix in loop 2 and disorder in loop 1, while a M297H variant that altered the properties of the electron transfer heme abolished reductive activation.

Feedback Valence Affects Auditory Perceptual Learning Independently of Feedback Probability

Science.gov (United States)

Amitay, Sygal; Moore, David R.; Molloy, Katharine; Halliday, Lorna F.

2015-01-01

Previous studies have suggested that negative feedback is more effective in driving learning than positive feedback. We investigated the effect on learning of providing varying amounts of negative and positive feedback while listeners attempted to discriminate between three identical tones; an impossible task that nevertheless produces robust learning. Four feedback conditions were compared during training: 90% positive feedback or 10% negative feedback informed the participants that they were doing equally well, while 10% positive or 90% negative feedback informed them they were doing equally badly. In all conditions the feedback was random in relation to the listeners’ responses (because the task was to discriminate three identical tones), yet both the valence (negative vs. positive) and the probability of feedback (10% vs. 90%) affected learning. Feedback that informed listeners they were doing badly resulted in better post-training performance than feedback that informed them they were doing well, independent of valence. In addition, positive feedback during training resulted in better post-training performance than negative feedback, but only positive feedback indicating listeners were doing badly on the task resulted in learning. As we have previously speculated, feedback that better reflected the difficulty of the task was more effective in driving learning than feedback that suggested performance was better than it should have been given perceived task difficulty. But contrary to expectations, positive feedback was more effective than negative feedback in driving learning. Feedback thus had two separable effects on learning: feedback valence affected motivation on a subjectively difficult task, and learning occurred only when feedback probability reflected the subjective difficulty. To optimize learning, training programs need to take into consideration both feedback valence and probability. PMID:25946173

Overlap valence quarks on a twisted mass sea. A case study for mixed action lattice QCD

International Nuclear Information System (INIS)

Cichy, Krzysztof; Herdoiza, Gregorio; UAM/CSIC Univ. Autonoma de Madrid

2012-11-01

We discuss a Lattice QCD mixed action investigation employing Wilson maximally twisted mass sea and overlap valence fermions. Using four values of the lattice spacing, we demonstrate that the overlap Dirac operator assumes a point-like locality in the continuum limit. We also show that by adopting suitable matching conditions for the sea and valence theories a consistent continuum limit for the pion decay constant and light baryon masses can be obtained. Finally, we confront results for sea-valence mixed meson masses and the valence scalar correlator with corresponding expressions of chiral perturbation theory. This allows us to extract low energy constants of mixed action chiral perturbation which characterize the strength of unitarity violations in our mixed action setup.

Overlap valence quarks on a twisted mass sea. A case study for mixed action lattice QCD

Energy Technology Data Exchange (ETDEWEB)

Cichy, Krzysztof [Deutsches Elektronen-Synchrotron (DESY), Zeuthen (Germany). John von Neumann-Inst. fuer Computing NIC; Poznan Univ. (Poland). Faculty of Physics; Drach, Vincent; Jansen, Karl [Deutsches Elektronen-Synchrotron (DESY), Zeuthen (Germany). John von Neumann-Inst. fuer Computing NIC; Garcia-Ramos, Elena [Deutsches Elektronen-Synchrotron (DESY), Zeuthen (Germany). John von Neumann-Inst. fuer Computing NIC; Humboldt-Universitaet, Berlin (Germany); Herdoiza, Gregorio [UAM/CSIC Univ. Autonoma de Madrid (Spain). Dept. de Fisica Teorica; UAM/CSIC Univ. Autonoma de Madrid (Spain). Inst. de Fisica Teorica; Collaboration: European Twisted Mass Collaboration

2012-11-15

We discuss a Lattice QCD mixed action investigation employing Wilson maximally twisted mass sea and overlap valence fermions. Using four values of the lattice spacing, we demonstrate that the overlap Dirac operator assumes a point-like locality in the continuum limit. We also show that by adopting suitable matching conditions for the sea and valence theories a consistent continuum limit for the pion decay constant and light baryon masses can be obtained. Finally, we confront results for sea-valence mixed meson masses and the valence scalar correlator with corresponding expressions of chiral perturbation theory. This allows us to extract low energy constants of mixed action chiral perturbation which characterize the strength of unitarity violations in our mixed action setup.

The extended variant of the bond valence-bond length correlation curve for boron(III)-oxygen bonds

International Nuclear Information System (INIS)

Sidey, Vasyl

2015-01-01

The extended variant of the bond valence (s)-bond length (r) correlation curve for boron(III)-oxygen bonds has been closely approximated using the three-parameter function s = [k/(r - l)] - m, where s is measured in valence units (vu), r is measured in Aa, k = 0.53 Aa.vu, l = 0.975(1) Aa and m = 0.32 vu. The function s = exp[(r 0 - r)/b] traditionally used in the modern bond valence model requires the separate set of the bond valence parameters (r 0 = 1.362 Aa; b = 0.23 Aa) in order to approximate the above s-r curve for the bonds shorter than ∝1.3 Aa.

Monoclonal antibodies to drosophila cytochrome P-450's

International Nuclear Information System (INIS)

Sundseth, S.S.; Kennel, S.J.; Waters, L.C.

1987-01-01

Hybridomas producing monoclonal antibodies were prepared by the fusion of SP2/0 myeloma cells and spleen cells from a female BALB/c mouse immunized by cytochrome P-450-A and P-450-B purified from Drosophila Hikone-R (BG) microsomes. P-450-A and P-450-B are electrophoretically distinct subsets of Drosophila P-450. P-450-A is ubiquitous among strains tested, while P-450-B is present in only a few strains displaying unique enzyme activities and increased insecticide resistance. The Oregon-R strain contains only cytochromes P-450-A and is susceptible to insecticides. The authors Hikone-R (BG) strain expresses both cytochromes P-450-A and P-450-B and is insecticide resistant. Antibody producing hybridomas were detected in a solid-phase radioimmunoassay (RIA) by binding to Hikone-R (BG) or Oregon-R microsomes. Four independent hybridomas were identified as producing monoclonal antibodies that recognized proteins in the P-450 complex by immunoblot experiments. Three monoclonal antibodies recognized P-450-A proteins, while one monoclonal antibody bound predominantly P-450-B. This monoclonal antibody also recognized southern armyworm (Spodoptera eridania, Cramer) microsomal proteins

Valence correlation in the s2d/sup n/, sd/sup n/+1, and d/sup n/+2 states of the first-row transition metal atoms

International Nuclear Information System (INIS)

Botch, B.H.; Dunning, T.H. Jr.; Harrison, J.F.

1981-01-01

The major differential valence correlation effects of the lowest lying states arising from the s 2 d/sup n/, sd/sup n/+1, and d/sup n/+2 configurations of the first-row transition metal atoms have been characterized using MCSCF and CI procedures. The important correlation effects are found to be, first, angular correlation of the 4s 2 pair arising because of the near degeneracy of the 4s and 4p orbitals and, second, radial correlation of the 3d electron pairs. This large differential radial correlation of the 3d electrons can be interpreted as being due to nonequivalent d orbitals in the sd/sup n/+1 and d/sup n/+2 excited states. Both of these effects can be incorporated into a simple MCSCF wave function that reduces the error in the excited state atomic dissociation limits (approx.0.2 eV in Sc--Cr and approx.0.5 eV in Mn--Cu for the sd/sup n/+1--s 2 d/sup n/ excitation energy), yet still is of a form which lends itself easily to molecular calculations

Low-temperature spin dynamics of a valence bond glass in Ba2YMoO6

Science.gov (United States)

de Vries, M. A.; Piatek, J. O.; Misek, M.; Lord, J. S.; Rønnow, H. M.; Bos, J.-W. G.

2013-04-01

We carried out ac magnetic susceptibility measurements and muon spin relaxation spectroscopy on the cubic double perovskite Ba2YMoO6, down to 50 mK. Below ∼1 K the muon relaxation is typical of a magnetic insulator with a spin-liquid type ground state, i.e. without broken symmetries or frozen moments. However, the ac susceptibility revealed a dilute-spin-glass-like transition below ∼1 K. Antiferromagnetically coupled Mo5+ 4d1 electrons in triply degenerate t2g orbitals are in this material arranged in a geometrically frustrated fcc lattice. Bulk magnetic susceptibility data has previously been interpreted in terms of a freezing to a heterogeneous state with non-magnetic sites where 4d1 electrons have paired in spin-singlets dimers, and residual unpaired Mo5+ 4d1 electron spins. Based on the magnetic heat capacity data it has been suggested that this heterogeneity is the result of kinetic constraints intrinsic to the physics of the pure system (possibly due to topological overprotection) leading to a self-induced glass of valence bonds between neighbouring 4d1 electrons. The muon spin relaxation (μSR) unambiguously points to a heterogeneous state with a static arrangement of unpaired electrons in a background of (valence bond) dimers between the majority of Mo5+ 4d electrons. The ac susceptibility data indicate that the residual magnetic moments freeze into a dilute-spin-glass-like state. This is in apparent contradiction with the muon-spin decoupling at 50 mK in fields up to 200 mT, which indicates that, remarkably, the time scale of the field fluctuations from the residual moments is ∼5 ns. Comparable behaviour has been observed in other geometrically frustrated magnets with spin-liquid-like behaviour and the implications of our observations on Ba2YMoO6 are discussed in this context.

Effect of carbon source on the accumulation of cytochrome P-450 in the yeast Saccharomyces cerevisiae.

Science.gov (United States)

Kärenlampi, S O; Marin, E; Hänninen, O O

1981-02-15

The appearance of cytochrome P-450 in the yeast Saccharomyces cerevisiae depended on the substrate supporting growth. Cytochrome P-450 was apparent in yeast cells grown on a strongly fermentable sugar such as D-glucose, D-fructose or sucrose. When yeast was grown on D-galactose, D-mannose or maltose, where fermentation and respiration occurred concomitantly, cytochrome P-450 was also formed. The cytochrome P-450 concentration was maximal at the beginning of the stationary phase of the culture. Thereafter the concentration decreased, reaching zero at a late-stationary phase. When the yeast was grown on a medium that contained lactose or pentoses (L-arabinose, L-rhamnose, D-ribose and D-xylose), cytochrome P-450 did not occur. When a non-fermentable energy source (glycerol, lactate or ethanol) was used, no cytochrome P-450 was detectable. Transfer of cells from D-glucose medium to ethanol medium caused a slow disappearance of cytochrome P-450, although the amount of the haemoprotein still continued to increase in the control cultures. Cytochrome P-450 appeared thus to accumulate in conditions where the rate of growth was fast and fermentation occurred. Occurrence of this haemoprotein is not necessarily linked, however, with the repression of mitochondrial haemoprotein synthesis.

Bond charge approximation for valence electron density in elemental semiconductors

International Nuclear Information System (INIS)

Bashenov, V.K.; Gorbachov, V.E.; Marvakov, D.I.

1985-07-01

The spatial valence electron distribution in silicon and diamond is calculated in adiabatic bond charge approximation at zero temperature when bond charges have the Gaussian shape and their tensor character is taken into account. An agreement between theory and experiment has been achieved. For this purpose Xia's ionic pseudopotentials and Schulze-Unger's dielectric function are used. By two additional parameters Asub(B) and Zsub(B)sup(') we describe the spatial extent of the bond charge and local-field corrections, respectively. The parameter Zsub(B)sup(') accounts for the ratio between the Coulomb and exchange correlation interactions of the valence electrons and its silicon and diamond values have different signs. (author)

Dimensionality and its effects upon the valence electronic structure of ordered metallic systems

International Nuclear Information System (INIS)

Tobin, J.G.

1983-07-01

The system c(10x2)Ag/Cu(001) was investigated with Angle-Resolved Photoemission (ARP), Low Energy Electron Diffraction (LEED) and Auger Electron Spectroscopy (AES). LEED and AES provided the calibration of a quartz microbalance used to measure the amount of silver evaporated onto the copper single crystal and also established the monolayer geometrical structure at one monolayer exposure. An off-normal ARP bandmapping study performed with polarized HeI and NeI radiation demonstrated the electronically two-dimensional nature of the silver d-bands at coverages of near one monolayer. The states at the surface Brillouin Zone center were assigned upon the basis of their polarization dependences and a structural model of hexagonal symmetry. A normal emission ARP experiment was performed at the Stanford Synchrotron Radiation Laboratory (SSRL) over the photon energy range of 6 to 32 eV. Data from it documented the evolution of the valence electronic structure of the silver overlayer from a two-dimensional hexagonal valence to a three-dimensional behavior converging towards that of bulk Ag(111). A structural study was attempted using the ARP technique of Normal Emission Photoelectron Diffraction over the photon energy range of 3.4 to 3.7 keV at SSRL, the results of which are inconclusive

Optical gain and gain suppression of quantum-well lasers with valence band mixing

International Nuclear Information System (INIS)

Ahn, D.; Chuang, S.L.

1990-01-01

The effects of valence band mixing on the nonlinear gains of quantum-well lasers are studied theoretically. The authors' analysis is based on the multiband effective-mass theory and the density matrix formalism with intraband relaxation taken into account. The gain and the gain-suppression coefficient of a quantum-well laser are calculated from the complex optical susceptibility obtained by the density matrix formulation with the theoretical dipole moments obtained from the multiband effective-mass theory. The calculated gain spectrum shows that there are remarkable differences (both in peak amplitude and spectral shape) between our model with valence band mixing and the conventional parabolic band model. The shape of the gain spectrum calculated by the authors' model becomes more symmetric due to intraband relaxation together with nonparabolic energy dispersions and is closer to the experimental observations when compared with the conventional method using the parabolic band model and the multiband effective-mass calculation without intraband relaxation. Both give quite asymmetric gain spectra. Optical intensity in the GaAs active region is estimated by solving rate equations for the stationary states with nonlinear gain suppression. The authors calculate the mode gain for the resonant mode including the gain suppression, which results in spectral hole burning of the gain spectrum

Structure of the Zymomonas mobilis respiratory chain: oxygen affinity of electron transport and the role of cytochrome c peroxidase.

Science.gov (United States)

Balodite, Elina; Strazdina, Inese; Galinina, Nina; McLean, Samantha; Rutkis, Reinis; Poole, Robert K; Kalnenieks, Uldis

2014-09-01

The genome of the ethanol-producing bacterium Zymomonas mobilis encodes a bd-type terminal oxidase, cytochrome bc1 complex and several c-type cytochromes, yet lacks sequences homologous to any of the known bacterial cytochrome c oxidase genes. Recently, it was suggested that a putative respiratory cytochrome c peroxidase, receiving electrons from the cytochrome bc1 complex via cytochrome c552, might function as a peroxidase and/or an alternative oxidase. The present study was designed to test this hypothesis, by construction of a cytochrome c peroxidase mutant (Zm6-perC), and comparison of its properties with those of a mutant defective in the cytochrome b subunit of the bc1 complex (Zm6-cytB). Disruption of the cytochrome c peroxidase gene (ZZ60192) caused a decrease of the membrane NADH peroxidase activity, impaired the resistance of growing culture to exogenous hydrogen peroxide and hampered aerobic growth. However, this mutation did not affect the activity or oxygen affinity of the respiratory chain, or the kinetics of cytochrome d reduction. Furthermore, the peroxide resistance and membrane NADH peroxidase activity of strain Zm6-cytB had not decreased, but both the oxygen affinity of electron transport and the kinetics of cytochrome d reduction were affected. It is therefore concluded that the cytochrome c peroxidase does not terminate the cytochrome bc1 branch of Z. mobilis, and that it is functioning as a quinol peroxidase. © 2014 The Authors.

Core-electron binding energies from self-consistent field molecular orbital theory using a mixture of all-electron real atoms and valence-electron model atoms

International Nuclear Information System (INIS)

Quinn, C.M.; Schwartz, M.E.

1981-01-01

The chemistry of large systems such as clusters may be readily investigated by valence-electron theories based on model potentials, but such an approach does not allow for the examination of core-electron binding energies which are commonly measured experimentally for such systems. Here we merge our previously developed Gaussian based valence-electron model potential theory with all-electron ab initio theory to allow for the calculation of core orbital binding energies when desired. For the atoms whose cores are to be examined, we use the real nuclear changes, all of the electrons, and the appropriate many-electron basis sets. For the rest of the system we use reduced nuclear charges, the Gaussian based model potentials, only the valence electrons, and appropriate valence-electron basis sets. Detailed results for neutral Al 2 are presented for the cases of all-electron, mixed real--model, and model--model SCF--MO calculations. Several different all-electron and valence electron calculations have been done to test the use of the model potential per se, as well as the effect of basis set choice. The results are in all cases in excellent agreement with one another. Based on these studies, a set of ''double-zeta'' valence and all-electron basis functions have been used for further SCF--MO studies on Al 3 , Al 4 , AlNO, and OAl 3 . For a variety of difference combinations of real and model atoms we find excellent agreement for relative total energies, orbital energies (both core and valence), and Mulliken atomic populations. Finally, direct core-hole-state ionic calculations are reported in detail for Al 2 and AlNO, and noted for Al 3 and Al 4 . Results for corresponding frozen-orbital energy differences, relaxed SCF--MO energy differences, and relaxation energies are in all cases in excellent agreement (never differing by more than 0.07 eV, usually by somewhat less). The study clearly demonstrates the accuracy of the mixed real--model theory

Fast prediction of cytochrome P450 mediated drug metabolism

DEFF Research Database (Denmark)

Rydberg, Patrik Åke Anders; Poongavanam, Vasanthanathan; Oostenbrink, Chris

2009-01-01

Cytochrome P450 mediated metabolism of drugs is one of the major determinants of their kinetic profile, and prediction of this metabolism is therefore highly relevant during the drug discovery and development process. A new rule-based method, based on results from density functional theory...... calculations, for predicting activation energies for aliphatic and aromatic oxidations by cytochromes P450 is developed and compared with several other methods. Although the applicability of the method is currently limited to a subset of P450 reactions, these reactions describe more than 90...

Open-Minded Midwifes, Literate Butchers, and Greedy Hooligans—The Independent Contributions of Stereotype Valence and Consistency on Evaluative Judgments

Science.gov (United States)

Schubert, Lisa; Körner, Anita; Lindau, Berit; Strack, Fritz; Topolinski, Sascha

2017-01-01

Do people evaluate an open-minded midwife less positively than a caring midwife? Both open-minded and caring are generally seen as positive attributes. However, consistency varies—the attribute caring is consistent with the midwife stereotype while open-minded is not. In general, both stimulus valence and consistency can influence evaluations. Six experiments investigated the respective influence of valence and consistency on evaluative judgments in the domain of stereotyping. In an impression formation paradigm, valence and consistency of stereotypic information about target persons were manipulated orthogonally and spontaneous evaluations of these target persons were measured. Valence reliably influenced evaluations. However, for strongly valenced stereotypes, no effect of consistency was observed. Parameters possibly preventing the occurrence of consistency effects were ruled out, specifically, valence of inconsistent attributes, processing priority of category information, and impression formation instructions. However, consistency had subtle effects on evaluative judgments if the information about a target person was not strongly valenced and experimental conditions were optimal. Concluding, in principle, both stereotype valence and consistency can play a role in evaluative judgments of stereotypic target persons. However, the more subtle influence of consistency does not seem to substantially influence evaluations of stereotyped target persons. Implications for fluency research and stereotype disconfirmation are discussed. PMID:29062289

Open-Minded Midwifes, Literate Butchers, and Greedy Hooligans-The Independent Contributions of Stereotype Valence and Consistency on Evaluative Judgments.

Science.gov (United States)

Schubert, Lisa; Körner, Anita; Lindau, Berit; Strack, Fritz; Topolinski, Sascha

2017-01-01

Do people evaluate an open-minded midwife less positively than a caring midwife? Both open-minded and caring are generally seen as positive attributes. However, consistency varies-the attribute caring is consistent with the midwife stereotype while open-minded is not. In general, both stimulus valence and consistency can influence evaluations. Six experiments investigated the respective influence of valence and consistency on evaluative judgments in the domain of stereotyping. In an impression formation paradigm, valence and consistency of stereotypic information about target persons were manipulated orthogonally and spontaneous evaluations of these target persons were measured. Valence reliably influenced evaluations. However, for strongly valenced stereotypes, no effect of consistency was observed. Parameters possibly preventing the occurrence of consistency effects were ruled out, specifically, valence of inconsistent attributes, processing priority of category information, and impression formation instructions. However, consistency had subtle effects on evaluative judgments if the information about a target person was not strongly valenced and experimental conditions were optimal. Concluding, in principle, both stereotype valence and consistency can play a role in evaluative judgments of stereotypic target persons. However, the more subtle influence of consistency does not seem to substantially influence evaluations of stereotyped target persons. Implications for fluency research and stereotype disconfirmation are discussed.

Open-Minded Midwifes, Literate Butchers, and Greedy Hooligans—The Independent Contributions of Stereotype Valence and Consistency on Evaluative Judgments

Directory of Open Access Journals (Sweden)

Lisa Schubert

2017-10-01

Full Text Available Do people evaluate an open-minded midwife less positively than a caring midwife? Both open-minded and caring are generally seen as positive attributes. However, consistency varies—the attribute caring is consistent with the midwife stereotype while open-minded is not. In general, both stimulus valence and consistency can influence evaluations. Six experiments investigated the respective influence of valence and consistency on evaluative judgments in the domain of stereotyping. In an impression formation paradigm, valence and consistency of stereotypic information about target persons were manipulated orthogonally and spontaneous evaluations of these target persons were measured. Valence reliably influenced evaluations. However, for strongly valenced stereotypes, no effect of consistency was observed. Parameters possibly preventing the occurrence of consistency effects were ruled out, specifically, valence of inconsistent attributes, processing priority of category information, and impression formation instructions. However, consistency had subtle effects on evaluative judgments if the information about a target person was not strongly valenced and experimental conditions were optimal. Concluding, in principle, both stereotype valence and consistency can play a role in evaluative judgments of stereotypic target persons. However, the more subtle influence of consistency does not seem to substantially influence evaluations of stereotyped target persons. Implications for fluency research and stereotype disconfirmation are discussed.

Electronic Connection Between the Quinone and Cytochrome c Redox Pools and Its Role in Regulation of Mitochondrial Electron Transport and Redox Signaling

Science.gov (United States)

Sarewicz, Marcin; Osyczka, Artur

2015-01-01

Mitochondrial respiration, an important bioenergetic process, relies on operation of four membranous enzymatic complexes linked functionally by mobile, freely diffusible elements: quinone molecules in the membrane and water-soluble cytochromes c in the intermembrane space. One of the mitochondrial complexes, complex III (cytochrome bc1 or ubiquinol:cytochrome c oxidoreductase), provides an electronic connection between these two diffusible redox pools linking in a fully reversible manner two-electron quinone oxidation/reduction with one-electron cytochrome c reduction/oxidation. Several features of this homodimeric enzyme implicate that in addition to its well-defined function of contributing to generation of proton-motive force, cytochrome bc1 may be a physiologically important point of regulation of electron flow acting as a sensor of the redox state of mitochondria that actively responds to changes in bioenergetic conditions. These features include the following: the opposing redox reactions at quinone catalytic sites located on the opposite sides of the membrane, the inter-monomer electronic connection that functionally links four quinone binding sites of a dimer into an H-shaped electron transfer system, as well as the potential to generate superoxide and release it to the intermembrane space where it can be engaged in redox signaling pathways. Here we highlight recent advances in understanding how cytochrome bc1 may accomplish this regulatory physiological function, what is known and remains unknown about catalytic and side reactions within the quinone binding sites and electron transfers through the cofactor chains connecting those sites with the substrate redox pools. We also discuss the developed molecular mechanisms in the context of physiology of mitochondria. PMID:25540143

Valence of facial cues influences sheep learning in a visual discrimination task

OpenAIRE

Bellegarde, Lucille; Erhard, Hans; Weiss, A.; Boissy, Alain; Haskell, M.J.

2017-01-01

Sheep are one of the most studied farm species in terms of their ability to process information from faces, but little is known about their face-based emotion recognition abilities. We investigated (a) whether sheep could use images of sheep faces taken in situation of varying valence as cues in a simultaneous discrimination task and (b) whether the valence of the situation affects their learning performance. To accomplish this, we photographed faces of sheep in three situations inducing emot...

Valence of Facial Cues Influences Sheep Learning in a Visual Discrimination Task

OpenAIRE

Lucille G. A. Bellegarde; Lucille G. A. Bellegarde; Lucille G. A. Bellegarde; Hans W. Erhard; Alexander Weiss; Alain Boissy; Marie J. Haskell

2017-01-01

Sheep are one of the most studied farm species in terms of their ability to process information from faces, but little is known about their face-based emotion recognition abilities. We investigated (a) whether sheep could use images of sheep faces taken in situation of varying valence as cues in a simultaneous discrimination task and (b) whether the valence of the situation affects their learning performance. To accomplish this, we photographed faces of sheep in three situations inducing emot...

Effect of carbon source on the accumulation of cytochrome P-450 in the yeast Saccharomyces cerevisiae.

OpenAIRE

Kärenlampi, S O; Marin, E; Hänninen, O O

1981-01-01

The appearance of cytochrome P-450 in the yeast Saccharomyces cerevisiae depended on the substrate supporting growth. Cytochrome P-450 was apparent in yeast cells grown on a strongly fermentable sugar such as D-glucose, D-fructose or sucrose. When yeast was grown on D-galactose, D-mannose or maltose, where fermentation and respiration occurred concomitantly, cytochrome P-450 was also formed. The cytochrome P-450 concentration was maximal at the beginning of the stationary phase of the culture...

Removal of Bound Triton X-100 from Purified Bovine Heart Cytochrome bc1

OpenAIRE

Varhač, Rastislav; Robinson, Neal C.; Musatov, Andrej

2009-01-01

Cytochrome bc1 isolated from Triton X-100 solubilized mitochondrial membranes contains up to 120 nmol of Triton X-100 bound per nmol of the enzyme. Purified cytochrome bc1 is fully active; however, protein bound Triton X-100 significantly interferes with structural studies of the enzyme. Removal of Triton X-100 bound to bovine cytochrome bc1 was accomplished by incubation with Bio-Beads SM-2 in presence of sodium cholate. Sodium cholate is critical since it does not interfere with the adsorpt...

A preliminary study on Fe valence of porcelain glaze by XAFS

International Nuclear Information System (INIS)

Zhang Maolin; Wang Changsui; Jin Pujun; Wei Shiqiang; Xu Wei; Chen Dongliang; Wu Ziyu

2008-01-01

Ru ware was a famous celadon in Song dynasty, whose structure analysis of glaze had always been a difficulty in scientifically analysis of ancient porcelains. The X-ray absorption fine structure spectrum (XAFS) of Fe element in glaze of Ru ware excavated in Qingliang temple was obtained. Fe valence state in porcelain glaze samples was stud/ed by Principle Component Analysis (PCA) along with linear combination fitting method. The main wavelength of the samples was also obtained by color/meter. The results show that the cyan glaze samples have great Fe 2+ /Fe 3+ , while the yellow glaze samples have small Fe 2+ /Fe 3+ . The work also showed that X-ray absorption fine structure spectrum was very suitable in nondestructive analysis of ancient ceramics. (authors)

Looking behaviour and preference for artworks: the role of emotional valence and location.

Science.gov (United States)

Kreplin, Ute; Thoma, Volker; Rodway, Paul

2014-10-01

The position of an item influences its evaluation, with research consistently finding that items occupying central locations are preferred and have a higher subjective value. The current study investigated whether this centre-stage effect (CSE) is a result of bottom-up gaze allocation to the central item, and whether it is affected by item valence. Participants (n=50) were presented with three images of artistic paintings in a row and asked to choose the image they preferred. Eye movements were recorded for a subset of participants (n=22). On each trial the three artworks were either similar but different, or were identical and with positive valence, or were identical and with negative valence. The results showed a centre-stage effect, with artworks in the centre of the row preferred, but only when they were identical and of positive valence. Significantly greater gaze allocation to the central and left artwork was not mirrored by equivalent increases in preference choices. Regression analyses showed that when the artworks were positive and identical the participants' last fixation predicted preference for the central art-work, whereas the fixation duration predicted preference if the images were different. Overall the result showed that item valence, rather than level of gaze allocation, influences the CSE, which is incompatible with the bottom-up gaze explanation. We propose that the centre stage heuristic, which specifies that the best items are in the middle, is able to explain these findings and the centre-stage effect. Copyright © 2014 Elsevier B.V. All rights reserved.

Mass spectrometry-based proteomic analysis of human liver cytochrome(s) P450

Energy Technology Data Exchange (ETDEWEB)

Shrivas, Kamlesh; Mindaye, Samuel T.; Getie-Kebtie, Melkamu; Alterman, Michail A., E-mail: Michail.Alterman@fda.hhs.gov

2013-02-15

The major objective of personalized medicine is to select optimized drug therapies and to a large degree such mission is determined by the expression profiles of cytochrome(s) P450 (CYP). Accordingly, a proteomic case study in personalized medicine is provided by the superfamily of cytochromes P450. Our knowledge about CYP isozyme expression on a protein level is very limited and based exclusively on DNA/mRNA derived data. Such information is not sufficient because transcription and translation events do not lead to correlated levels of expressed proteins. Here we report expression profiles of CYPs in human liver obtained by mass spectrometry (MS)-based proteomic approach. We analyzed 32 samples of human liver microsomes (HLM) of different sexes, ages and ethnicity along with samples of recombinant human CYPs. We have experimentally confirmed that each CYP isozyme can be effectively differentiated by their unique isozyme-specific tryptic peptide(s). Trypsin digestion patterns for almost 30 human CYP isozymes were established. Those findings should assist in selecting tryptic peptides suitable for MS-based quantitation. The data obtained demonstrate remarkable differences in CYP expression profiles. CYP2E1, CYP2C8 and CYP4A11 were the only isozymes found in all HLM samples. Female and pediatric HLM samples revealed much more diverse spectrum of expressed CYPs isozymes compared to male HLM. We have confirmed expression of a number of “rare” CYP (CYP2J2, CYP4B1, CYP4V2, CYP4F3, CYP4F11, CYP8B1, CYP19A1, CYP24A1 and CYP27A1) and obtained first direct experimental data showing expression of such CYPs as CYP2F1, CYP2S1, CYP2W1, CYP4A22, CYP4X1, and CYP26A1 on a protein level. - Highlights: ► First detailed proteomic analysis of CYP isozymes expression in human liver ► Trypsin digestion patterns for almost 30 human CYP isozymes established ► The data obtained demonstrate remarkable differences in CYP expression profiles. ► Female HLM samples revealed more

Mass spectrometry-based proteomic analysis of human liver cytochrome(s) P450

International Nuclear Information System (INIS)

Shrivas, Kamlesh; Mindaye, Samuel T.; Getie-Kebtie, Melkamu; Alterman, Michail A.

2013-01-01

The major objective of personalized medicine is to select optimized drug therapies and to a large degree such mission is determined by the expression profiles of cytochrome(s) P450 (CYP). Accordingly, a proteomic case study in personalized medicine is provided by the superfamily of cytochromes P450. Our knowledge about CYP isozyme expression on a protein level is very limited and based exclusively on DNA/mRNA derived data. Such information is not sufficient because transcription and translation events do not lead to correlated levels of expressed proteins. Here we report expression profiles of CYPs in human liver obtained by mass spectrometry (MS)-based proteomic approach. We analyzed 32 samples of human liver microsomes (HLM) of different sexes, ages and ethnicity along with samples of recombinant human CYPs. We have experimentally confirmed that each CYP isozyme can be effectively differentiated by their unique isozyme-specific tryptic peptide(s). Trypsin digestion patterns for almost 30 human CYP isozymes were established. Those findings should assist in selecting tryptic peptides suitable for MS-based quantitation. The data obtained demonstrate remarkable differences in CYP expression profiles. CYP2E1, CYP2C8 and CYP4A11 were the only isozymes found in all HLM samples. Female and pediatric HLM samples revealed much more diverse spectrum of expressed CYPs isozymes compared to male HLM. We have confirmed expression of a number of “rare” CYP (CYP2J2, CYP4B1, CYP4V2, CYP4F3, CYP4F11, CYP8B1, CYP19A1, CYP24A1 and CYP27A1) and obtained first direct experimental data showing expression of such CYPs as CYP2F1, CYP2S1, CYP2W1, CYP4A22, CYP4X1, and CYP26A1 on a protein level. - Highlights: ► First detailed proteomic analysis of CYP isozymes expression in human liver ► Trypsin digestion patterns for almost 30 human CYP isozymes established ► The data obtained demonstrate remarkable differences in CYP expression profiles. ► Female HLM samples revealed more

Two Parallel Pathways Assign Opposing Odor Valences during Drosophila Memory Formation

Directory of Open Access Journals (Sweden)

Daisuke Yamazaki

2018-02-01

Full Text Available During olfactory associative learning in Drosophila, odors activate specific subsets of intrinsic mushroom body (MB neurons. Coincident exposure to either rewards or punishments is thought to activate extrinsic dopaminergic neurons, which modulate synaptic connections between odor-encoding MB neurons and MB output neurons to alter behaviors. However, here we identify two classes of intrinsic MB γ neurons based on cAMP response element (CRE-dependent expression, γCRE-p and γCRE-n, which encode aversive and appetitive valences. γCRE-p and γCRE-n neurons act antagonistically to maintain neutral valences for neutral odors. Activation or inhibition of either cell type upsets this balance, toggling odor preferences to either positive or negative values. The mushroom body output neurons, MBON-γ5β′2a/β′2mp and MBON-γ2α′1, mediate the actions of γCRE-p and γCRE-n neurons. Our data indicate that MB neurons encode valence information, as well as odor information, and this information is integrated through a process involving MBONs to regulate learning and memory.

Organ donation video messaging: differential appeal, emotional valence, and behavioral intention.

Science.gov (United States)

Rodrigue, J R; Fleishman, A; Vishnevsky, T; Fitzpatrick, S; Boger, M

2014-10-01

Video narratives increasingly are used to draw the public's attention to the need for more registered organ donors. We assessed the differential impact of donation messaging videos on appeal, emotional valence, and organ donation intentions in 781 non-registered adults. Participants watched six videos (four personal narratives, one informational video without personal narrative, and one unrelated to donation) with or without sound (subtitled), randomly sequenced to minimize order effects. We assessed appeal, emotional valence, readiness to register as organ donors, and donation information-seeking behavior. Compared to other video types, one featuring a pediatric transplant recipient (with or without sound) showed more favorable appeal (p emotional valence (p emotion (OR = 1.05, 95% CI = 1.03, 1.07, p < 0.001) were significant multivariable predictors of clicking through to the donation website. Brief, one-min videos can have a very dramatic and positive impact on willingness to consider donation and behavioral intentions to register as an organ donor. © 2014 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Enhanced conflict-driven cognitive control by emotional arousal, not by valence.

Science.gov (United States)

Zeng, Qinghong; Qi, Senqing; Li, Miaoyun; Yao, Shuxia; Ding, Cody; Yang, Dong

2017-09-01

Emotion is widely agreed to have two dimensions, valence and arousal. Few studies have explored the effect of emotion on conflict adaptation by considering both of these, which could have dissociate influence. The present study aimed to fill the gap as to whether emotional valence and arousal would exert dissociable influence on conflict adaptation. In the experiments, we included positive, neutral, and negative conditions, with comparable arousal between positive and negative conditions. Both positive and negative conditions have higher arousal than neutral ones. In Experiment 1, by using a two-colour-word Flanker task, we found that conflict adaptation was enhanced in both positive and negative contexts compared to a neutral context. Furthermore, this effect still existed when controlling stimulus-response repetitions in Experiment 2, which used a four-colour-word Flanker task. The findings suggest emotional arousal enhances conflict adaptation, regardless of emotional valence. Thus, future studies should consider emotional arousal when studying the effect of emotion on conflict adaptation. Moreover, the unique role of the emotional context in conflict-driven cognitive control is emphasised.

Valence bond solids for SU(n) spin chains: Exact models, spinon confinement, and the Haldane gap

International Nuclear Information System (INIS)

Greiter, Martin; Rachel, Stephan

2007-01-01

To begin with, we introduce several exact models for SU(3) spin chains: First is a translationally invariant parent Hamiltonian involving four-site interactions for the trimer chain, with a threefold degenerate ground state. We provide numerical evidence that the elementary excitations of this model transform under representation 3 of SU(3) if the original spins of the model transform under representation 3. Second is a family of parent Hamiltonians for valence bond solids of SU(3) chains with spin representations 6, 10, and 8 on each lattice site. We argue that of these three models, only the latter two exhibit spinon confinement and, hence, a Haldane gap in the excitation spectrum. We generalize some of our models to SU(n). Finally, we use the emerging rules for the construction of valence bond solid states to argue that models of antiferromagnetic chains of SU(n) spins, in general, possess a Haldane gap if the spins transform under a representation corresponding to a Young tableau consisting of a number of boxes λ which is divisible by n. If λ and n have no common divisor, the spin chain will support deconfined spinons and not exhibit a Haldane gap. If λ and n have a common divisor different from n, it will depend on the specifics of the model including the range of the interaction

Cytochrome b5 and epoxide hydrolase contribute to benzo[a]pyrene-DNA adduct formation catalyzed by cytochrome P450 1A1 under low NADPH:P450 oxidoreductase conditions

International Nuclear Information System (INIS)

Stiborová, Marie; Moserová, Michaela; Černá, Věra; Indra, Radek; Dračínský, Martin; Šulc, Miroslav; Henderson, Colin J.; Wolf, C. Roland; Schmeiser, Heinz H.; Phillips, David H.; Frei, Eva; Arlt, Volker M.

2014-01-01

In previous studies we had administered benzo[a]pyrene (BaP) to genetically engineered mice (HRN) which do not express NADPH:cytochrome P450 oxidoreductase (POR) in hepatocytes and observed higher DNA adduct levels in livers of these mice than in wild-type mice. To elucidate the reason for this unexpected finding we have used two different settings for in vitro incubations; hepatic microsomes from control and BaP-pretreated HRN mice and reconstituted systems with cytochrome P450 1A1 (CYP1A1), POR, cytochrome b 5 , and epoxide hydrolase (mEH) in different ratios. In microsomes from BaP-pretreated mice, in which Cyp1a1 was induced, higher levels of BaP metabolites were formed, mainly of BaP-7,8-dihydrodiol. At a low POR:CYP1A1 ratio of 0.05:1 in the reconstituted system, the amounts of BaP diones and BaP-9-ol formed were essentially the same as at an equimolar ratio, but formation of BaP-3-ol was ∼1.6-fold higher. Only after addition of mEH were BaP dihydrodiols found. Two BaP-DNA adducts were formed in the presence of mEH, but only one when CYP1A1 and POR were present alone. At a ratio of POR:CYP1A1 of 0.05:1, addition of cytochrome b 5 increased CYP1A1-mediated BaP oxidation to most of its metabolites indicating that cytochrome b 5 participates in the electron transfer from NADPH to CYP1A1 required for enzyme activity of this CYP. BaP-9-ol was formed even by CYP1A1 reconstituted with cytochrome b 5 without POR. Our results suggest that in livers of HRN mice Cyp1a1, cytochrome b 5 and mEH can effectively activate BaP to DNA binding species, even in the presence of very low amounts of POR

Vection Modulates Emotional Valence of Autobiographical Episodic Memories

Science.gov (United States)

Seno, Takeharu; Kawabe, Takahiro; Ito, Hiroyuki; Sunaga, Shoji

2013-01-01

We examined whether illusory self-motion perception ("vection") induced by viewing upward and downward grating motion stimuli can alter the emotional valence of recollected autobiographical episodic memories. We found that participants recollected positive episodes more often while perceiving upward vection. However, when we tested a small moving…

Valence holes observed in nanodiamonds dispersed in water

Science.gov (United States)

Petit, Tristan; Pflüger, Mika; Tolksdorf, Daniel; Xiao, Jie; Aziz, Emad F.

2015-02-01

Colloidal dispersion is essential for most nanodiamond applications, but its influence on nanodiamond electronic properties remains unknown. Here we have probed the electronic structure of oxidized detonation nanodiamonds dispersed in water by using soft X-ray absorption and emission spectroscopies at the carbon and oxygen K edges. Upon dispersion in water, the π* transitions from sp2-hybridized carbon disappear, and holes in the valence band are observed.Colloidal dispersion is essential for most nanodiamond applications, but its influence on nanodiamond electronic properties remains unknown. Here we have probed the electronic structure of oxidized detonation nanodiamonds dispersed in water by using soft X-ray absorption and emission spectroscopies at the carbon and oxygen K edges. Upon dispersion in water, the π* transitions from sp2-hybridized carbon disappear, and holes in the valence band are observed. Electronic supplementary information (ESI) available: Experimental methods, details on XAS/XES normalization and background correction procedures. See DOI: 10.1039/c4nr06639a

Name-valence and physical attractiveness in Facebook: their compensatory effects on friendship acceptance.

Science.gov (United States)

Greitemeyer, Tobias; Kunz, Irene

2013-01-01

Name-valence and physical attractiveness have been shown to be associated with how people respond toward others, in that people judge and behave more positively toward individuals with positive names and individuals who are physically attractive. The present research examined whether Facebook users are more likely to accept friendship requests from other Facebook users with positive (relative to negative) names and who are physically attractive (relative to being moderately attractive). In fact, both name-valence and physical attractiveness affected friendship acceptance. Moreover, results revealed that name-valence can be compensated by physical attractiveness (and vice versa). Acceptance rates of requests from users with positive names who are moderately attractive, as well as requests from users with negative names who are attractive did not significantly differ from those with positive names who are attractive.

The chemical bond in inorganic chemistry the bond valence model

CERN Document Server

Brown, I David

2016-01-01

The bond valence model is a version of the ionic model in which the chemical constraints are expressed in terms of localized chemical bonds formed by the valence charge of the atoms. Theorems derived from the properties of the electrostatic flux predict the rules obeyed by both ionic and covalent bonds. They make quantitative predictions of coordination number, crystal structure, bond lengths and bond angles. Bond stability depends on the matching of the bonding strengths of the atoms, while the conflicting requirements of chemistry and space lead to the structural instabilities responsible for the unusual physical properties displayed by some materials. The model has applications in many fields ranging from mineralogy to molecular biology.

Polarography of cytochrome c in ammoniacal buffers containing cobalt ions. The effect of the protein conformation.

Science.gov (United States)

Brabec, V

1985-12-01

Catalytic currents yielded by cytochrome c in ammoniacal buffers containing cobalt ions at a dropping mercury electrode (Brdicka's catalytic currents) were investigated by means of direct current, differential pulse, normal pulse (NP) and phase-selective alternating current polarography. It was found that Brdicka's catalytic current of cytochrome c, (the more negative part of Brdicka's double wave, wave B) is influenced by the presence of cytochrome c denaturants in the background solution. The wave B rose with the increasing concentrations of urea and sodium perchlorate, and increased in parallel with absorbance changes at 409 and 695 nm measured for identical cytochrome c solutions. The latter absorbance changes reflect unfolding of cytochrome c molecules in the bulk of solution by these denaturants. The results of NP polarography (a technique working with large potential excursion during the drop lifetime) indicate that in Brdicka's solution cytochrome c could extensively be unfolded due to its adsorption at the mercury electrode, polarized to potentials around that of zero charge.

Barrier-free proton transfer in the valence anion of 2'-deoxyadenosine-5'-monophosphate. II. A computational study

Science.gov (United States)

Kobyłecka, Monika; Gu, Jiande; Rak, Janusz; Leszczynski, Jerzy

2008-01-01

The propensity of four representative conformations of 2'-deoxyadenosine-5'-monophosphate (5'-dAMPH) to bind an excess electron has been studied at the B3LYP /6-31++G(d,p) level. While isolated canonical adenine does not support stable valence anions in the gas phase, all considered neutral conformations of 5'-dAMPH form adiabatically stable anions. The type of an anionic 5'-dAMPH state, i.e., the valence, dipole bound, or mixed (valence/dipole bound), depends on the internal hydrogen bond(s) pattern exhibited by a particular tautomer. The most stable anion results from an electron attachment to the neutral syn-south conformer. The formation of this anion is associated with a barrier-free proton transfer triggered by electron attachment and the internal rotation around the C4'-C5' bond. The adiabatic electron affinity of the a&barbelow;south-syn anion is 1.19eV, while its vertical detachment energy is 1.89eV. Our results are compared with the photoelectron spectrum (PES) of 5'-dAMPH- measured recently by Stokes et al., [J. Chem. Phys. 128, 044314 (2008)]. The computational VDE obtained for the most stable anionic structure matches well with the experimental electron binding energy region of maximum intensity. A further understanding of DNA damage might require experimental and computational studies on the systems in which purine nucleotides are engaged in hydrogen bonding.

Use of Raman spectroscopy to study reduction state of mitochondrial cytochromes in an isolated heart under normoxic and hypoxic conditions

DEFF Research Database (Denmark)

Brazhe, N. A.; Treiman, M.; Faricelli, B.

2013-01-01

to 1606 cm-1). As expected from a decreased reduction of electron transport chain upon uncoupling, the presence of FCCP in the perfusion caused a decrease in the intensity of cytochromal peaks with no change of Mb peaks. Global stop-flow ischemia of 35 min elicited a progressive increase in the intensity...

Emotional Valence, Arousal, and Threat Ratings of 160 Chinese Words among Adolescents.

Science.gov (United States)

Ho, Samuel M Y; Mak, Christine W Y; Yeung, Dannii; Duan, Wenjie; Tang, Sandy; Yeung, June C; Ching, Rita

2015-01-01

This study was conducted to provide ratings of valence/pleasantness, arousal/excitement, and threat/potential harm for 160 Chinese words. The emotional valence classification (positive, negative, or neutral) of all of the words corresponded to that of the equivalent English language words. More than 90% of the participants, junior high school students aged between 12 and 17 years, understood the words. The participants were from both mainland China and Hong Kong, thus the words can be applied to adolescents familiar with either simplified (e.g. in mainland China) or traditional Chinese (e.g. in Hong Kong) with a junior secondary school education or higher. We also established eight words with negative valence, high threat, and high arousal ratings to facilitate future research, especially on attentional and memory biases among individuals prone to anxiety. Thus, the new emotional word list provides a useful source of information for affective research in the Chinese language.

Theoretical study of singlet oxygen molecule generation via an exciplex with valence-excited thiophene.

Science.gov (United States)

Sumita, Masato; Morihashi, Kenji

2015-02-05

Singlet-oxygen [O2((1)Δg)] generation by valence-excited thiophene (TPH) has been investigated using multireference Møller-Plesset second-order perturbation (MRMP2) theory of geometries optimized at the complete active space self-consistent field (CASSCF) theory level. Our results indicate that triplet TPH(1(3)B2) is produced via photoinduced singlet TPH(2(1)A1) because 2(1)A1 TPH shows a large spin-orbit coupling constant with the first triplet excited state (1(3)B2). The relaxed TPH in the 1(3)B2 state can form an exciplex with O2((3)Σg(-)) because this exciplex is energetically more stable than the relaxed TPH. The formation of the TPH(1(3)B2) exciplex with O2((3)Σg(-)) whose total spin multiplicity is triplet (T1 state) increases the likelihood of transition from the T1 state to the singlet ground or first excited singlet state. After the transition, O2((1)Δg) is emitted easily although the favorable product is that from a 2 + 4 cycloaddition reaction.

Temperature effects in the valence fluctuation of europium intermetallic compounds

International Nuclear Information System (INIS)

Menezes, O.L.T. de; Troper, A.; Gomes, A.A.

1978-03-01

A previously reported model for valence fluctuations in europium compound in order to account for thermal occupation effect. Experimental results are critically discussed and new experiments are suggested

Pion and kaon valence-quark parton quasidistributions

Science.gov (United States)

Xu, Shu-Sheng; Chang, Lei; Roberts, Craig D.; Zong, Hong-Shi

2018-05-01

Algebraic Ansätze for the Poincaré-covariant Bethe-Salpeter wave functions of the pion and kaon are used to calculate their light-front wave functions, parton distribution amplitudes, parton quasidistribution amplitudes, valence parton distribution functions, and parton quasidistribution functions (PqDFs). The light-front wave functions are broad, concave functions, and the scale of flavor-symmetry violation in the kaon is roughly 15%, being set by the ratio of emergent masses in the s - and u -quark sectors. Parton quasidistribution amplitudes computed with longitudinal momentum Pz=1.75 GeV provide a semiquantitatively accurate representation of the objective parton distribution amplitude, but even with Pz=3 GeV , they cannot provide information about this amplitude's end point behavior. On the valence-quark domain, similar outcomes characterize PqDFs. In this connection, however, the ratio of kaon-to-pion u -quark PqDFs is found to provide a good approximation to the true parton distribution function ratio on 0.4 ≲x ≲0.8 , suggesting that with existing resources computations of ratios of parton quasidistributions can yield results that support empirical comparison.

Valence and lowest Rydberg electronic states of phenol investigated by synchrotron radiation and theoretical methods

Energy Technology Data Exchange (ETDEWEB)

Limão-Vieira, P., E-mail: plimaovieira@fct.unl.pt; Ferreira da Silva, F.; Lange, E. [Laboratório de Colisões Atómicas e Moleculares, CEFITEC, Departamento de Física, Faculdade de Ciências e Tecnologia, Universidade NOVA de Lisboa, 2829-516 Caparica (Portugal); Duflot, D. [Univ. Lille, UMR 8523–Physique des Lasers Atomes et Molécules, F-59000 Lille (France); CNRS, UMR 8523, F-59000 Lille (France); Jones, N. C.; Hoffmann, S. V. [ISA, Department of Physics and Astronomy, Aarhus University, Ny Munkegade 120, DK-8000 Aarhus C (Denmark); Śmiałek, M. A. [Department of Control and Power Engineering, Faculty of Ocean Engineering and Ship Technology, Gdańsk University of Technology, Gabriela Narutowicza 11/12, 80-233 Gdańsk (Poland); Department of Physical Sciences, The Open University, Walton Hall, MK7 6AA Milton Keynes (United Kingdom); Jones, D. B. [School of Chemical and Physical Sciences, Flinders University, GPO Box 2100, Adelaide, SA 5001 (Australia); Brunger, M. J. [School of Chemical and Physical Sciences, Flinders University, GPO Box 2100, Adelaide, SA 5001 (Australia); Institute of Mathematical Sciences, University of Malaya, 50603 Kuala Lumpur (Malaysia)

2016-07-21

We present the experimental high-resolution vacuum ultraviolet (VUV) photoabsorption spectra of phenol covering for the first time the full 4.3–10.8 eV energy-range, with absolute cross sections determined. Theoretical calculations on the vertical excitation energies and oscillator strengths were performed using time-dependent density functional theory and the equation-of-motion coupled cluster method restricted to single and double excitations level. These have been used in the assignment of valence and Rydberg transitions of the phenol molecule. The VUV spectrum reveals several new features not previously reported in the literature, with particular reference to the 6.401 eV transition, which is here assigned to the 3sσ/σ{sup ∗}(OH)←3π(3a″) transition. The measured absolute photoabsorption cross sections have been used to calculate the photolysis lifetime of phenol in the earth’s atmosphere (0–50 km).

Effect of a pH Gradient on the Protonation States of Cytochrome c Oxidase: A Continuum Electrostatics Study.

Science.gov (United States)

Magalhães, Pedro R; Oliveira, A Sofia F; Campos, Sara R R; Soares, Cláudio M; Baptista, António M

2017-02-27

Cytochrome c oxidase (CcO) couples the reduction of dioxygen to water with transmembrane proton pumping, which leads to the generation of an electrochemical gradient. In this study we analyze how one of the components of the electrochemical gradient, the difference in pH across the membrane, or ΔpH, influences the protonation states of residues in CcO. We modified our continuum electrostatics/Monte Carlo (CE/MC) method in order to include the ΔpH and applied it to the study of CcO, in what is, to our best knowledge, the first CE/MC study of CcO in the presence of a pH gradient. The inclusion of a transmembrane pH gradient allows for the identification of residues whose titration behavior depends on the pH on both sides of the membrane. Among the several residues with unusual titration profiles, three are well-known key residues in the proton transfer process of CcO: E286 I , Y288 I , and K362 I . All three residues have been previously identified as being critical for the catalytic or proton pumping functions of CcO. Our results suggest that when the pH gradient increases, these residues may be part of a regulatory mechanism to stem the proton flow.

The Synthesis of NiO/TiO2 Heterostructures and Their Valence Band Offset Determination

Directory of Open Access Journals (Sweden)

Z. H. Ibupoto

2014-01-01

Full Text Available In this work, a heterojunction based on p-type NiO/n-type TiO2 nanostructures has been prepared on the fluorine doped tin oxide (FTO glass substrate by hydrothermal method. Scanning electron microscopy (SEM and X-Ray diffraction techniques were used for the morphological and crystalline arrays characterization. The X-ray photoelectron spectroscopy was employed to determine the valence-band offset (VBO of the NiO/TiO2 heterojunction prepared on FTO glass substrate. The core levels of Ni 2p and Ti 2p were utilized to align the valence-band offset of p-type NiO/n-type TiO2 heterojunction. The valence band offset was found to be ∼0.41 eV and the conduction band was calculated about ∼0.91 eV. The ratio of conduction band offset and the valence-band offset was found to be 2.21.

Distinct populations of neurons respond to emotional valence and arousal in the human subthalamic nucleus.

Science.gov (United States)

Sieger, Tomáš; Serranová, Tereza; Růžička, Filip; Vostatek, Pavel; Wild, Jiří; Štastná, Daniela; Bonnet, Cecilia; Novák, Daniel; Růžička, Evžen; Urgošík, Dušan; Jech, Robert

2015-03-10

Both animal studies and studies using deep brain stimulation in humans have demonstrated the involvement of the subthalamic nucleus (STN) in motivational and emotional processes; however, participation of this nucleus in processing human emotion has not been investigated directly at the single-neuron level. We analyzed the relationship between the neuronal firing from intraoperative microrecordings from the STN during affective picture presentation in patients with Parkinson's disease (PD) and the affective ratings of emotional valence and arousal performed subsequently. We observed that 17% of neurons responded to emotional valence and arousal of visual stimuli according to individual ratings. The activity of some neurons was related to emotional valence, whereas different neurons responded to arousal. In addition, 14% of neurons responded to visual stimuli. Our results suggest the existence of neurons involved in processing or transmission of visual and emotional information in the human STN, and provide evidence of separate processing of the affective dimensions of valence and arousal at the level of single neurons as well.

Spin dynamics and magnetic ordering in mixed valence systems

International Nuclear Information System (INIS)

Shapiro, S.M.; Moller, H.B.; Axe, J.D.; Birgeneau, R.J.; Bucher, E.

1977-01-01

Neutron scattering measurements are reported on the mixed valence compounds Ce/sub 1-x/Th/sub x/ and TmSe. The Chi''(Q,ω) as derived from the inelastic spectra of Ce 0 . 74 Th 0 . 26 shows a peak in the γ phase near 20.0 meV and shifts abruptly to greater than 70.0 meV at the transition to the α phase. The temperature independence of the susceptibility within the γ phase cannot be simply reconciled with the temperature dependence of the valence within the γ phase. TmSe is shown to order in a type I antiferromagnetic structure below T/sub N/ approx. 3.2 K. The magnetic phase diagram is understood as a successive domain reorientation and a metamagnetic phase transition for T 3+ orders in a type II structure but never achieves long range order

Evidence that Na+-pumping occurs through the D-channel in Vitreoscilla cytochrome bo

International Nuclear Information System (INIS)

Kim, Seong K.; Stark, Benjamin C.; Webster, Dale A.

2005-01-01

The operon (cyo) encoding the Na + -pumping respiratory terminal oxidase (cytochrome bo) of the bacterium Vitreoscilla was transformed into Escherichia coli GV100, a deletion mutant of cytochrome bo. This was done for the wild type operon and five mutants in three conserved Cyo subunit I amino acids known to be crucial for H + transport in the E. coli enzyme, one near the nuclear center, one in the K-channel, and one in the D-channel. CO-binding, NADH and ubiquinol oxidase, and Na + -pumping activities were all substantially inhibited by each mutation. The wild type Vitreoscilla cytochrome bo can pump Na + against a concentration gradient, resulting in a transmembrane concentration differential of 2-3 orders of magnitude. It is proposed that Vitreoscilla cytochrome bo pumps four Na + through the D-channel to the exterior and transports four H + through the K-channel for the reduction of each O 2

Quadrupole moments of high spin states in the trans lead region

International Nuclear Information System (INIS)

Neyens, G.; Hardeman, F.; Nouwen, R.; S'heeren, G.; Van Den Bergh, M.; Cousement, R.

1990-01-01

The last few years, a lot of attention has been paid to the trans lead region. A reason for this has to be found in the fact that 208 Pb is a double magic core: both its proton and neutron shell are closed. This means that all nuclei in the lead region can be described well by the shell model, using a spherical 208 Pb core (spherical symmetric potential) and some valence particles or holes around it. The question is whether this model is also correct for high spin states. In this region, isomers with high angular momenta can only be created by alignment of all the spins of the valence particles and holes. And in some cases, alignment is not enough: core excitations are necessary to build up the large spin value of the isomeric state (e.g. the 63/2-isomer in 211 Rn. This means that a neutron pair from the closed N = 126 shell is broken up and one or both neutrons are excited to a level with higher energy and spin. The alignment of the valence-particle-spins causes an increase of the interactions between the valence particles (holes) on one hand, and between the valence particles (holes) and the hard core on the other hand. The latter interaction can cause a deformation of the core. The two interactions are taken into account in two different models: The SERI model (Spherical shell model with Empirical Residual Interactions) and the DIPM (Deformed Independent Particle Model). This paper reports that the effect of alignment of the spins of the valence particles in an isomeric state has been taken into account in the shell model by using residual interactions between the valence particles. These interactions are introduced in the theory in an empirical way or are calculated. Another model, the DIPM, takes into account the effect of alignment in a natural way: it starts from a deformed core (e.g. an axial symmetric potential) in which the valence particles are moving independently from each other)

Coordinate regulation of cytochrome and alternative pathway respiration in tobacco.

Science.gov (United States)

Vanlerberghe, G C; McIntosh, L

1992-12-01

In suspension cells of NT1 tobacco (Nicotiana tabacum L. cv bright yellow), inhibition of the cytochrome pathway of respiration with antimycin A induced a large increase in the capacity of the alternative pathway over a period of approximately 12 h, as confirmed in both whole cells and isolated mitochondria. The increase in alternative pathway capacity required de novo RNA and protein synthesis and correlated closely with the increase of a 35-kD alternative oxidase protein. When the cytochrome pathway of intact cells was inhibited by antimycin A, respiration proceeded exclusively through the alternative pathway, reached rates significantly higher than before antimycin A addition, and was not stimulated by p-trifluoromethoxycarbonylcyanide (FCCP). When inhibition of the cytochrome pathway was relieved, alternative pathway capacity and the level of the 35-kD alternative oxidase protein declined. Respiration rate also declined and could once again be stimulated by FCCP. These observations show that the capacities of the mitochondrial electron transport pathways can be regulated in a coordinate fashion.

Unique organizational and functional features of the cytochrome c maturation system in Shewanella oneidensis.

Directory of Open Access Journals (Sweden)

Miao Jin

Full Text Available Shewanella are renowned for their ability to respire on a wide range of electron acceptors, which has been partially accredited to the presence of a large number of the c-type cytochromes. In the model species S. oneidensis MR-1, at least 41 genes encode c-type cytochromes that are predicted to be intact, thereby likely functional. Previously, in-frame deletion mutants for 36 of these genes were obtained and characterized. In this study, first we completed the construction of an entire set of c-type cytochrome mutants utilizing a newly developed att-based mutagenesis approach, which is more effective and efficient than the approach used previously by circumventing the conventional cloning. Second, we investigated the cytochrome c maturation (Ccm system in S. oneidensis. There are two loci predicted to encode components of the Ccm system, SO0259-SO0269 and SO0476-SO0478. The former is proven essential for cytochrome c maturation whereas the latter is dispensable. Unlike the single operon organization observed in other γ-proteobacteria, genes at the SO0259-SO0269 locus are uniquely organized into four operons, ccmABCDE, scyA, SO0265, and ccmFGH-SO0269. Functional analysis revealed that the SO0265 gene rather than the scyA and SO0269 genes are relevant to cytochrome c maturation.

Experimental Constraints on the Partitioning and Valence of V and Cr in Garnet and Coexisting Glass

Science.gov (United States)

Righter, K.; Sutton, S.; Berthet, S.; Newville, M.

2008-01-01

A series of experiments with garnet and coexisting melt have been carried out across a range of oxygen fugacities (near hematite-magnetite (HM) to below the iron-wustite (IW) buffers) at 1.7 GPa to study the partitioning and valence of Cr and V in both phases. Experiments were carried out in a non end loaded piston cylinder apparatus, and the run products were analyzed with electron microprobe and xray absorption near edge structure (XANES) analysis at beamline 13-ID at the Advanced Photon Source of Argonne National Lab. The valence of vanadium and chromium were determined using the position and intensity of the Ka pre-edge peaks, calibrated on a series of Cr and Vbearing standard glasses. This technique has been applied to V and Cr in glasses and V in spinels previously, and in these isotropic phases there are no orientational effects on the XANES spectra (Righter et al., 2006, Amer. Mineral. 91, 1643-1656). We also now demonstrate this to be true for V and Cr in garnet. Also, previous work has shown that V has a higher valence in the glass (or melt) than in the coexisting spinel. This is also true for V in garnet-glass pairs in this study. Vanadium valence in garnets varies from 2.7 below the IW buffer to 3.7 near HM, and for coexisting glass it varies from 3.2 to 4.3. Vanadium valence measured in some natural garnets from mantle localities indicates V in the more reduced range at 2.5. Comparisons will be made between fO2 estimated from V valence and other methods for garnet-bearing mantle samples. In contrast, Cr valence measured in garnet and coexisting glass for all experimental and natural samples is 2.9- 3.0, suggesting that the valence of Cr does not vary within either phase across a large fO2 range. These results demonstrate that while V varies from 2+ to 3+ to 4+ in garnet-melt systems, Cr does not, and this will ultimately affect the partitioning behavior of these two elements in natural systems. Garnet/melt D(Cr) are between 12 and 17 across this range

Prediction of activation energies for aromatic oxidation by cytochrome P450

DEFF Research Database (Denmark)

Rydberg, Patrik; Ryde, Ulf; Olsen, Lars

2008-01-01

We have estimated the activation energy for aromatic oxidation by compound I in cytochrome P450 for a diverse set of 17 substrates using state-of-the-art density functional theory (B3LYP) with large basis sets. The activation energies vary from 60 to 87 kJ/mol. We then test if these results can...... be reproduced by computationally less demanding methods. The best methods (a B3LYP calculation of the activation energy of a methoxy-radical model or a partial least-squares model of the semiempirical AM1 bond dissociation energies and spin densities of the tetrahedral intermediate for both a hydroxyl...

D. C. electric field behavior of high lying states in atomic uranium

International Nuclear Information System (INIS)

Paisner, J.A.; Carlson, L.R.; Worden, E.F.; Johnson, S.A.; May, C.A.; Solarz, R.W.

1976-01-01

The effects of D. C. electric fields on high lying Rydberg and valence states in atomic uranium have been studied. Results of measurements of Stark shifts, lifetime lengthening via l-mixing, critical fields for ionization, barrier tunneling, and the appearance of zero-field parity forbidden transitions are presented for atomic uranium along with the observation of field induced autoionization of valence states. 3 figs

Pressure induced valence transitions in the Anderson lattice model

International Nuclear Information System (INIS)

Bernhard, B.H.; Coqblin, B.

2009-01-01

We apply the equation of motion method to the Anderson lattice model, which describes the physical properties of heavy fermion compounds. In particular, we focus here on the variation of the number of f electrons with pressure, associated to the crossover from the Kondo regime to the intermediate valence regime. We treat here the non-magnetic case and introduce an improved approximation, which consists of an alloy analogy based decoupling for the Anderson lattice model. It is implemented by partial incorporation of the spatial correlations contained in higher-order Green's functions involved in the problem that have been formerly neglected. As it has been verified in the framework of the Hubbard model, the alloy analogy avoids the breakdown of sum rules and is more appropriate to explore the asymmetric case of the periodic Anderson Hamiltonian. The densities of states for a simple cubic lattice are calculated for various values of the model parameters V, t, E f , and U.

If You Don't Have Valence, Ask Your Neighbor: Evaluation of Neutral Words as a Function of Affective Semantic Associates.

Science.gov (United States)

Kuhlmann, Michael; Hofmann, Markus J; Jacobs, Arthur M

2017-01-01

How do humans perform difficult forced-choice evaluations, e.g., of words that have been previously rated as being neutral? Here we tested the hypothesis that in this case, the valence of semantic associates is of significant influence. From corpus based co-occurrence statistics as a measure of association strength we computed individual neighborhoods for single neutral words comprised of the 10 words with the largest association strength. We then selected neutral words according to the valence of the associated words included in the neighborhoods, which were either mostly positive, mostly negative, mostly neutral or mixed positive and negative, and tested them using a valence decision task (VDT). The data showed that the valence of semantic neighbors can predict valence judgments to neutral words. However, all but the positive neighborhood items revealed a high tendency to elicit negative responses. For the positive and negative neighborhood categories responses congruent with the neighborhood's valence were faster than incongruent responses. We interpret this effect as a semantic network process that supports the evaluation of neutral words by assessing the valence of the associative semantic neighborhood. In this perspective, valence is considered a semantic super-feature, at least partially represented in associative activation patterns of semantic networks.