1000 resultados para REDOX INTERACTIONS
Resumo:
A fundamental interaction for electrons is their hyperfine interaction (HFI) with nuclear spins. HFI is well characterized in free atoms and molecules, and is crucial for purposes from chemical identification of atoms to trapped ion quantum computing. However, electron wave functions near atomic sites, therefore HFI, are often not accurately known in solids. Here we perform an all-electron calculation for conduction electrons in silicon and obtain reliable information on HFI. We verify the outstanding quantum spin coherence in Si, which is critical for fault-tolerant solid state quantum computing.
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The energy barrier distribution E(b) of five samples with different concentrations x of Ni nanoparticles using scaling plots from ac magnetic susceptibility data has been determined. The scaling of the imaginary part of the susceptibility chi""(v, T) versus T ln (iota t/tau(0)) remains valid for all samples, which display Ni nanoparticles with similar shape and size. The mean value < E(b)> increases appreciably with increasing x, or more appropriately with increasing dipolar interactions between Ni nanoparticles. We argue that such an increase in < E(b)> constitutes a powerful tool for quality control in magnetic recording media technology where the dipolar interaction plays an important role. (c) 2011 American Institute of Physics. [doi: 10.1063/1.3533911]
Resumo:
The role of dipolar interactions among Ni nanoparticles (NPs) embedded in an amorphous SiO(2)/C matrix with different concentrations has been studied performing ac magnetic susceptibility chi(ac) measurements. For very diluted samples, with Ni concentrations < 4 wt % Ni or very weak dipolar interactions, the data are well described by the Neacuteel-Arrhenius law. Increasing Ni concentration to values up to 12.8 wt % Ni results in changes in the Neacuteel-Arrhenius behavior, the dipolar interactions become important, and need to be considered to describe the magnetic response of the NPs system. We have found no evidence of a spin-glasslike behavior in our Ni NP systems even when dipolar interactions are clearly present.
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The MINOS experiment at Fermilab has recently reported a tension between the oscillation results for neutrinos and antineutrinos. We show that this tension, if it persists, can be understood in the framework of nonstandard neutrino interactions (NSI). While neutral current NSI (nonstandard matter effects) are disfavored by atmospheric neutrinos, a new charged current coupling between tau neutrinos and nucleons can fit the MINOS data without violating other constraints. In particular, we show that loop-level contributions to flavor-violating tau decays are sufficiently suppressed. However, conflicts with existing bounds could arise once the effective theory considered here is embedded into a complete renormalizable model. We predict the future sensitivity of the T2K and NOvA experiments to the NSI parameter region favored by the MINOS fit, and show that both experiments are excellent tools to test the NSI interpretation of the MINOS data.
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We study the spin-1/2 Ising model on a Bethe lattice in the mean-field limit, with the interaction constants following one of two deterministic aperiodic sequences, the Fibonacci or period-doubling one. New algorithms of sequence generation were implemented, which were fundamental in obtaining long sequences and, therefore, precise results. We calculate the exact critical temperature for both sequences, as well as the critical exponents beta, gamma, and delta. For the Fibonacci sequence, the exponents are classical, while for the period-doubling one they depend on the ratio between the two exchange constants. The usual relations between critical exponents are satisfied, within error bars, for the period-doubling sequence. Therefore, we show that mean-field-like procedures may lead to nonclassical critical exponents.
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We present a scheme for quasiperfect transfer of polariton states from a sender to a spatially separated receiver, both composed of high-quality cavities filled by atomic samples. The sender and the receiver are connected by a nonideal transmission channel -the data bus- modelled by a network of lossy empty cavities. In particular, we analyze the influence of a large class of data-bus topologies on the fidelity and transfer time of the polariton state. Moreover, we also assume dispersive couplings between the polariton fields and the data-bus normal modes in order to achieve a tunneling-like state transfer. Such a tunneling-transfer mechanism, by which the excitation energy of the polariton effectively does not populate the data-bus cavities, is capable of attenuating appreciably the dissipative effects of the data-bus cavities. After deriving a Hamiltonian for the effective coupling between the sender and the receiver, we show that the decay rate of the fidelity is proportional to a cooperativity parameter that weighs the cost of the dissipation rate against the benefit of the effective coupling strength. The increase of the fidelity of the transfer process can be achieved at the expense of longer transfer times. We also show that the dependence of both the fidelity and the transfer time on the network topology is analyzed in detail for distinct regimes of parameters. It follows that the data-bus topology can be explored to control the time of the state-transfer process.
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A technique is proposed for creating nonground-state Bose-Einstein condensates in a trapping potential by means of the temporal modulation of atomic interactions. Applying a time-dependent spatially homogeneous magnetic field modifies the atomic scattering length. A modulation of the scattering length excites the condensate, which, under special conditions, can be transferred to an excited nonlinear coherent mode. It is shown that a phase-transition-like behavior occurs in the time-averaged population imbalance between the ground and excited states. The application of the technique is analyzed and it is shown that the considered effect can be realized for experimentally available condensates.
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We report electron-paramagnetic resonance (EPR) studies at similar to 9.5 GHz (X band) and similar to 34 GHz (Q band) of powder and single-crystal samples of the compound Cu(2)[TzTs](4) [N-thiazol-2-yl-toluenesulfonamidatecopper(II)], C(40)H(36)Cu(2)N(8)O(8)S(8), having copper(II) ions in dinuclear units. Our data allow determining an antiferromagnetic interaction J(0)=(-113 +/- 1) cm(-1) (H(ex)=-J(0)S(1)center dot S(2)) between Cu(II) ions in the dinuclear unit and the anisotropic contributions to the spin-spin coupling matrix D (H(ani)=S(1)center dot D center dot S(2)), a traceless symmetric matrix with principal values D/4=(0.198 +/- 0.003) cm(-1) and E/4=(0.001 +/- 0.003) cm(-1) arising from magnetic dipole-dipole and anisotropic exchange couplings within the units. In addition, the single-crystal EPR measurements allow detecting and estimating very weak exchange couplings between neighbor dinuclear units, with an estimated magnitude parallel to J(')parallel to=(0.060 +/- 0.015) cm(-1). The interactions between a dinuclear unit and the ""environment"" of similar units in the structure of the compound produce a spin dynamics that averages out the intradinuclear dipolar interactions. This coupling with the environment leads to decoherence, a quantum phase transition that collapses the dipolar interaction when the isotropic exchange coupling with neighbor dinuclear units equals the magnitude of the intradinuclear dipolar coupling. Our EPR experiments provide a new procedure to follow the classical exchange-narrowing process as a shift and collapse of the line structure (not only as a change of the resonance width), which is described with general (but otherwise simple) theories of magnetic resonance. Using complementary procedures, our EPR measurements in powder and single-crystal samples allow measuring simultaneously three types of interactions differing by more than three orders of magnitude (between 113 cm(-1) and 0.060 cm(-1)).
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We introduce an analytical approximation scheme to diagonalize parabolically confined two-dimensional (2D) electron systems with both the Rashba and Dresselhaus spin-orbit interactions. The starting point of our perturbative expansion is a zeroth-order Hamiltonian for an electron confined in a quantum wire with an effective spin-orbit induced magnetic field along the wire, obtained by properly rotating the usual spin-orbit Hamiltonian. We find that the spin-orbit-related transverse coupling terms can be recast into two parts W and V, which couple crossing and noncrossing adjacent transverse modes, respectively. Interestingly, the zeroth-order Hamiltonian together with W can be solved exactly, as it maps onto the Jaynes-Cummings model of quantum optics. We treat the V coupling by performing a Schrieffer-Wolff transformation. This allows us to obtain an effective Hamiltonian to third order in the coupling strength k(R)l of V, which can be straightforwardly diagonalized via an additional unitary transformation. We also apply our approach to other types of effective parabolic confinement, e. g., 2D electrons in a perpendicular magnetic field. To demonstrate the usefulness of our approximate eigensolutions, we obtain analytical expressions for the nth Landau-level g(n) factors in the presence of both Rashba and Dresselhaus couplings. For small values of the bulk g factors, we find that spin-orbit effects cancel out entirely for particular values of the spin-orbit couplings. By solving simple transcendental equations we also obtain the band minima of a Rashba-coupled quantum wire as a function of an external magnetic field. These can be used to describe Shubnikov-de Haas oscillations. This procedure makes it easier to extract the strength of the spin-orbit interaction in these systems via proper fitting of the data.
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The concept of constitutional dynamic chemistry (CDC) based on the control of non-covalent interactions in supramolecular structures is promising for having a large impact on nanoscience and nanotechnology if adequate nanoscale manipulation methods are used. In this study, we demonstrate that the layer-by-layer (LbL) technique may be used to produce electroactive electrodes with ITO coated by tetrasulfonated nickel phthalocyanine (NiTsPc) alternated with poly(allylamine hydrochloride) (PAH) incorporating gold nanoparticles (AuNP), in which synergy has been achieved in the interaction between the nanoparticles and NiTsPc. The catalytic activity toward hydrogen peroxide (H(2)O(2)) in multilayer films was investigated using cyclic voltammetry, where oxidation of H(2)O(2) led to increased currents in the PAH-AuNP/NiTsPc films for the electrochemical processes associated with the phthalocyanine ring and nickel at 0.52 and 0.81 V vs. SCE, respectively, while for PAH/NiTsPc films (without AuNP) only the first redox process was affected. In control experiments we found out that the catalytic activity was not solely due to the presence of AuNP, but rather to the nanoparticles inducing NiTsPc supramolecular structures that favored access to their redox sites, thus yielding strong charge transfer. The combined effects of NiTsPc and AuNP, which could only be observed in nanostructured LbL films, point to another avenue to pursue within the CDC paradigm.
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The thermo-solvatochromism of 2,6-dibromo-4-[(E)-2-(1-methylpyridinium-4-yl)ethenyl] phenolate, MePMBr(2), has been studied in mixtures of water, W, with ionic liquids, ILs, in the temperature range of 10 to 60 degrees C, where feasible. The objectives of the study were to test the applicability of a recently introduced solvation model, and to assess the relative importance of solute-solvent solvophobic interactions. The ILs were 1-allyl-3-alkylimidazolium chlorides, where the alkyl groups are methyl, 1-butyl, and 1-hexyl, respectively. The equilibrium constants for the interaction of W and the ILs were calculated from density data; they were found to be linearly dependent on N(C), the number of carbon atoms of the alkyl group; van't Hoff equation (log K versus 1/T) applied satisfactorily. Plots of the empirical solvent polarities, E(T) (MePMBr(2)) in kcal mol(-1), versus the mole fraction of water in the binary mixture, chi(w), showed non-linear, i.e., non-ideal behavior. The dependence of E(T) (MePMBr(2)) on chi(w), has been conveniently quantified in terms of solvation by W, IL, and the ""complex"" solvent IL-W. The non-ideal behavior is due to preferential solvation by the IL and, more efficiently, by IL-W. The deviation from linearity increases as a function of increasing N(C) of the IL, and is stronger than that observed for solvation of MePMBr(2) by aqueous 1-propanol, a solvent whose lipophilicity is 12.8 to 52.1 times larger than those of the ILs investigated. The dependence on N(C) is attributed to solute-solvent solvophobic interactions, whose relative contribution to solvation are presumably greater than that in mixtures of water and 1-propanol.
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Biogeochemistry is hosting this special thematic issue devoted to studies of land-water interactions, as part of the Large-scale Biosphere-Atmosphere Experiment in Amaznia (LBA). This compilation of papers covers a broad range of topics with a common theme of coupling land and water processes, across pristine and impacted systems. Findings highlighted that hydrologic flowpaths are clearly important across basin size and structure in determining how water and solutes reach streams. Land-use changes have pronounced impacts on flowpaths, and subsequently, on stream chemistry, from small streams to large rivers. Carbon is produced and transformed across a broad array of fluvial environments and wetlands. Surface waters are not only driven by, but provide feedback to, the atmosphere.
Resumo:
No-till (NT) adoption is an essential tool for development of sustainable agricultural systems, and how NT affects the soil organic C (SOC) dynamics is a key component of these systems. The effect of a plow tillage (PT) and NT age chronosequence on SOC concentration and interactions with soil fertility were assessed in a variable charge Oxisol, located in the South Center quadrant of Parana State, Brazil (50 degrees 23`W and 24 degrees 36`S). The chronosequence consisted of the following six sites: (i) native field (NF); (ii) PT of the native field (PNF-1) involving conversion of natural vegetation to cropland; (iii) NT for 10 years (NT-10); (iv) NT for 20 years (NT-20); (v) NT for 22 years (NT-22); and (vi) conventional tillage for 22 years (CT-22) involving PT with one disking after summer harvest and one after winter harvest to 20 cm depth plus two harrow disking. Soil samples were collected from five depths (0-2.5; 2.5-5; 5-10; 10-20; and 20-40 cm) and SOC, pH (in H(2)O and KCl), Delta pH, potential acidity, exchangeable bases, and cation exchangeable capacity (CEC) were measured. An increase in SOC concentration positively affected the pH, the negative charge and the CEC and negatively impacted potential acidity. Regression analyses indicated a close relationship between the SOC concentration and other parameters measured in this study. The regression fitted between SOC concentration and CEC showed a close relationship. There was an increase in negative charge and CEC with increase in SOC concentration: CEC increased by 0.37 cmol(c) kg(-1) for every g of C kg(-1) soil. The ratio of ECEC:SOC was 0.23 cmol(c) kg(-1) for NF and increased to 0.49 cmol(c) kg(-1) for NT-22. The rates of P and K for 0-10 cm depth increased by 9.66 kg ha(-1) yr(-1) and 17.93 kg ha(-1) yr(-1), respectively, with NF as a base line. The data presented support the conclusion that long-term NT is a useful strategy for improving fertility of soils with variable charge. (C) 2008 Elsevier B.V. All rights reserved.
Resumo:
The ubiquitin-proteasome system governs the half-life of most cellular proteins. Calorie restriction (CR) extends the maximum life span of a variety of species and prevents oxidized protein accumulation. We studied the effects of CR on the ubiquitin-proteasome system and protein turnover in aging Saccharomyces cerevisiae. CR increased chronological life span as well as proteasome activity compared to control cells. The levels of protein carbonyls, a marker of protein oxidation, and those of polyubiquitinated proteins were modulated by CR. Controls, but not CR cells, exhibited a significant increase in oxidized proteins. In keeping with decreased proteasome activity, polyubiquitinated proteins were increased in young control cells compared to time-matched CR cells, but were profoundly decreased in aged control cells despite decreased proteasomal activity. This finding is related to a decreased polyubiquitination ability due to the impairment of the ubiquitin-activating enzyme in aged control cells, probably related to a more oxidative microenvironment. CR preserves the ubiquitin-proteasome system activity. Overall, we found that aging and CR modulate many aspects of protein modification and turnover. (C) 2011 Elsevier Inc. All rights reserved.
Resumo:
Exercise training is known to promote relevant changes in the properties of skeletal muscle contractility toward powerful fibers. However, there are few studies showing the effect of a well-established exercise training protocol on Ca(2+) handling and redox status in skeletal muscles with different fiber-type compositions. We have previously standardized a valid and reliable protocol to improve endurance exercise capacity in mice based on maximal lactate steady-state workload (MLSSw). The aim of this study was to investigate the effect of exercise training, performed at MLSSw, on the skeletal muscle Ca(2+) handling-related protein levels and cellular redox status in soleus and plantaris. Male C57BL/6J mice performed treadmill training at MLSSw over a period of eight weeks. Muscle fiber-typing was determined by myosin ATPase histochemistry, citrate synthase activity by spectrophotometric assay, Ca(2+) handling-related protein levels by Western blot and reduced to oxidized glutathione ratio (GSH:GSSG) by high-performance liquid chromatography. Trained mice displayed higher running performance and citrate synthase activity compared with untrained mice. Improved running performance in trained mice was paralleled by fast-to-slow fiber-type shift and increased capillary density in both plantaris and soleus. Exercise training increased dihydropyridine receptor (DHPR) alpha 2 subunit, ryanodine receptor and Na(+)/Ca(2+) exchanger levels in plantaris and soleus. Moreover, exercise training elevated DHPR beta 1 subunit and sarcoplasmic reticulum Ca(2+)-ATPase (SERCA) 1 levels in plantaris and SERCA2 levels in soleus of trained mice. Skeletal muscle GSH content and GSH:GSSG ratio was increased in plantaris and soleus of trained mice. Taken together, our findings indicate that MLSSw exercise-induced better running performance is, in part, due to increased levels of proteins involved in skeletal muscle Ca(2+) handling, whereas this response is partially dependent on specificity of skeletal muscle fiber-type composition. Finally, we demonstrated an augmented cellular redox status and GSH antioxidant capacity in trained mice.