Detection of catechol using mixed Langmuir-Blodgett films of a phospholipid and phthalocyanines as voltammetric sensors

The combination of metallic phthalocyanines (MPcs) and biomolecules has been explored in the literature either as mimetic systems to investigate molecular interactions or as supporting layers to immobilize biomolecules. Here, Langmuir-Blodgett (LB) films containing the phospholipid dimyristoyl phosphatidic acid (DMPA) mixed either with iron phthalocyanine (FePc) or with lutetium bisphthalocyanine (LuPc(2)) were applied as ITO modified-electrodes in the detection of catechol using cyclic voltammetry. The mixed Langmuir films of FePc + DMPA and LuPc(2) + DMPA displayed surface-pressure isotherms with no evidence of molecular-level interactions. The Fourier Transform Infrared (FTIR) spectra of the multilayer LB films confirmed the lack of interaction between the components. The DMPA and the FePc molecules were found to be oriented perpendicularly to the substrate, while LuPc(2) molecules were randomly organized. The phospholipid matrix induced a remarkable electrocatalytic effect on the phthalocyanines; as a result the mixed LB films deposited on ITO could be used to detect catechol with detection limits of 4.30 x 10(-7) and 3.34 x 10(-7) M for FePc + DMPA and LuPc(2) + DMPA, respectively. Results from kinetics experiments revealed that ion diffusion dominated the response of the modified electrodes. The sensitivity was comparable to that of other non-enzymatic sensors, which is sufficient to detect catechol in the food industry. The higher stability of the electrochemical response of the LB films and the ability to control the molecular architecture are promising for further studies with incorporation of biomolecules.

Generation of nonground-state Bose-Einstein condensates by modulating atomic interactions

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.

Finite-size corrections to entanglement in quantum critical systems

We analyze the finite-size corrections to entanglement in quantum critical systems. By using conformal symmetry and density functional theory, we discuss the structure of the finite-size contributions to a general measure of ground state entanglement, which are ruled by the central charge of the underlying conformal field theory. More generally, we show that all conformal towers formed by an infinite number of excited states (as the size of the system L -> infinity) exhibit a unique pattern of entanglement, which differ only at leading order (1/L)(2). In this case, entanglement is also shown to obey a universal structure, given by the anomalous dimensions of the primary operators of the theory. As an illustration, we discuss the behavior of pairwise entanglement for the eigenspectrum of the spin-1/2 XXZ chain with an arbitrary length L for both periodic and twisted boundary conditions.

State protection under collective damping and diffusion

In this paper we provide a recipe for state protection in a network of oscillators under collective damping and diffusion. Our strategy is to manipulate the network topology, i.e., the way the oscillators are coupled together, the strength of their couplings, and their natural frequencies, in order to create a relaxation-diffusion-free channel. This protected channel defines a decoherence-free subspace (DFS) for nonzero-temperature reservoirs. Our development also furnishes an alternative approach to build up DFSs that offers two advantages over the conventional method: it enables the derivation of all the network-protected states at once, and also reveals, through the network normal modes, the mechanism behind the emergence of these protected domains.

Anomalous Rashba spin-orbit interaction in InAs/GaSb quantum wells

We theoretically investigate the Rashba spin-orbit interaction in InAs/GaSb quantum wells (QWs). We find that the Rashba spin-splitting (RSS) sensitively depends on the thickness of the InAs layer. The RSS exhibits nonlinear behavior for narrow InAs/GaSb QWs and the oscillating feature for wide InAs/GaSb QWs. The nonlinear and oscillating behaviors arise from the weakened and enhanced interband coupling. The RSS also show asymmetric features respect to the direction of the external electric field. (C) 2008 American Institute of Physics.

Isotropic and anisotropic spin-spin interactions and a quantum phase transition in a dinuclear Cu(II) compound

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)).

Energy spectra for quantum wires and two-dimensional electron gases in magnetic fields with Rashba and Dresselhaus spin-orbit interactions

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.

Molecular dynamics simulation of liquid trimethylphosphine

Structural and dynamical properties of liquid trimethylphosphine (TMP), (CH(3))(3)P, as a function of temperature is investigated by molecular dynamics (MD) simulations. The force field used in the MD simulations, which has been proposed from molecular mechanics and quantum chemistry calculations, is able to reproduce the experimental density of liquid TMP at room temperature. Equilibrium structure is investigated by the usual radial distribution function, g(r), and also in the reciprocal space by the static structure factor, S(k). On the basis of center of mass distances, liquid TMP behaves like a simple liquid of almost spherical particles, but orientational correlation due to dipole-dipole interactions is revealed at short-range distances. Single particle and collective dynamics are investigated by several time correlation functions. At high temperatures, diffusion and reorientation occur at the same time range as relaxation of the liquid structure. Decoupling of these dynamic properties starts below ca. 220 K, when rattling dynamics of a given TMP molecules due to the cage effect of neighbouring molecules becomes important. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3624408]

Polarization effects in molecular dynamics simulations of glass-formers Ca(NO(3))(2)center dot nH(2)O, n=4, 6, and 8

Thermodynamics, equilibrium structure, and dynamics of glass-forming liquids Ca(NO(3))(2)center dot nH(2)O, n=4, 6, and 8, have been investigated by molecular dynamics (MD) simulations. A polarizable model was considered for H(2)O and NO(3)- on the basis of previous fluctuating charge models for pure water and the molten salt 2Ca(NO(3))(2)center dot 3KNO(3). Similar thermodynamic properties have been obtained with nonpolarizable and polarizable models. The glass transition temperature, T(g), estimated from MD simulations was dependent on polarization, in particular the dependence of T(g) with electrolyte concentration. Significant polarization effects on equilibrium structure were observed in cation-cation, cation-anion, and water-water structures. Polarization increases the diffusion coefficient of H(2)O, but does not change significantly the diffusion coefficients of ions. Viscosity decreases upon inclusion of polarization, but the conductivity calculated with the polarizable model is smaller than the nonpolarizable model because polarization enhances anion-cation interactions.

Thermo-solvatochromism in binary mixtures of water and ionic liquids: on the relative importance of solvophobic interactions

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.

Land-Water interactions in the amazon

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.

Soil organic carbon and fertility interactions affected by a tillage chronosequence in a Brazilian Oxisol

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.

An opinion dynamics model for the diffusion of innovations

We study the dynamics of the adoption of new products by agents with continuous opinions and discrete actions (CODA). The model is such that the refusal in adopting a new idea or product is increasingly weighted by neighbor agents as evidence against the product. Under these rules, we study the distribution of adoption times and the final proportion of adopters in the population. We compare the cases where initial adopters are clustered to the case where they are randomly scattered around the social network and investigate small world effects on the final proportion of adopters. The model predicts a fat tailed distribution for late adopters which is verified by empirical data. (C) 2009 Elsevier B.V. All rights reserved.

Generic hyperbolicity of stationary solutions for a reaction-diffusion system

In this paper, we study the generic hyperbolicity of equilibria of a reaction-diffusion system with respect to nonlinear terms in the set of C(2)-functions equipped with the Whitney Topology. To accomplish this, we combine Baire`s Lemma and the usual Transversality Theorem. (C) 2010 Elsevier Ltd. All rights reserved.

THE SUMMATION OF VOLUNTARY AND ELECTRICAL ELICITED STIMULUS INCREASES JOINT TORQUE?

The aim of this study is to analyze the effect of neuromuscular electrical stimulation (NMES) on myoelectrical activity and on joint torque during isometric plantar flexion contraction. Ten healthy young adult subjects participate in this study. The electrodes for NMES are placed along posterior thigh along ciatic nerve trajectory. It is measured the myoelectrical activity and the isometric torque generated by ankle plantar flexion with an isokinetic dynamometer. The conditions of isometric contractions are maximum isometric voluntary contraction (MIVC), NMES, and association of both (MIVC+NMES). The results show lower torque during NMES and larger SOL activity compare to the others. Besides, in order to keep the same objective task (to produce the same level of torque), neuromuscular adaptations are necessary on the common drive.