Descripción: Fil:Flexer, V. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina.

Descripción: The linear response within the elimination of the small component formalism is aimed at obtaining the leading order relativistic corrections to magnetic molecular properties in the context of the elimination of the small component approximation. In the present work we extend the method in order to include two-body effects in the form of a mean field one-body operator. To this end we consider the four-component Dirac-Hartree-Fock operator as the starting point in the evaluation of the second order relativistic expression of magnetic properties. The approach thus obtained is the fully consistent leading order approximation of the random phase approximation four-component formalism. The mean field effect on the relativistic corrections to both the diamagnetic and paramagnetic terms of magnetic properties taking into account both the Coulomb and Breit two-body interactions is considered. © 2006 American Institute of Physics.

Descripción: A theoretical study of the relation between the relativistic formulation of the nuclear magnetic shielding and spin-rotation tensors is presented. To this end a theoretical expression of the relativistic spin-rotation tensor is formulated, considering a molecular Hamiltonian of relativistic electrons and non-relativistic nuclei. Molecular rotation effects are introduced considering the terms of the Born-Oppenheimer decomposition, which couple the electrons and nuclei dynamics. The loss of the simple relation linking both spectral parameters in the non-relativistic formulation is further analyzed carrying out a perturbative expansion of relativistic effects by means of the linear response within the elimination of the small component approach. It is concluded that relativistic effects on the spin-rotation tensor are less important than those of the nuclear magnetic shielding tensor. © 2012 American Institute of Physics.

Descripción: In the present work a set of formal relations connecting different approaches to calculate relativistic effects on magnetic molecular properties are proven. The linear response (LR) within the elimination of the small component (ESC), Breit Pauli, and minimal-coupling approaches are compared. To this end, the leading order ESC reduction of operators within the minimal-coupling four-component approach is carried out. The equivalence of all three approaches within the ESC approximation is proven. It is numerically verified for the NMR nuclear-magnetic shielding tensor taking HX and C H3 X (X=Br,I) as model compounds. Formal relations proving the gauge origin invariance of the full relativistic effect on the NMR nuclear-magnetic shielding tensor within the LR-ESC approach are presented. © 2006 American Institute of Physics.

Descripción: Ring polymer molecular dynamics experiments have been carried out to examine effects derived from nuclear quantum fluctuations at ambient conditions on equilibrium and non-equilibrium dynamical characteristics of charge solvation by a popular simple, rigid, water model, SPC/E, and for a more recent, and flexible, q-TIP4P/F model, to examine the generality of conclusions. In particular, we have recorded the relaxation of the solvent energy gap following instantaneous, ±e charge jumps in an initially uncharged Lennard-Jones-like solute. In both charge cases, quantum effects are reflected in sharper decays at the initial stages of the relaxation, which produce up to a ∼20% reduction in the characteristic timescales describing the solvation processes. For anionic solvation, the magnitude of polarization fluctuations controlling the extent of the water proton localization in the first solvation shell is somewhat more marked than for cations, bringing the quantum solvation process closer to the classical case. Effects on the solvation response from the explicit incorporation of flexibility in the water Hamiltonian are also examined. Predictions from linear response theories for the overall relaxation profile and for the corresponding characteristic timescales are reasonably accurate for the solvation of cations, whereas we find that they are much less satisfactory for the anionic case. © 2013 AIP Publishing LLC.

Descripción: We present a theoretical study on the inner-shell ionization of Au, Pb, and Bi. A collective response model, the shellwise local plasma approximation (SLPA), is employed, which works within the dielectric formalism. The wave functions and binding energies were obtained in fully-relativistic way by solving numerically the Dirac equation. The theoretical results describe nicely the experimental data for M-shell ionization of Au and Bi above 2MeV/amu, and for L-shell ionization of Au and Pb above 10 MeV/amu. The SLPA tends to underestimate the data for energies below the range of validity of the model and approach to them for higher energies.

Descripción: In the present work, numerical results of the nuclear spin-rotation (SR) tensor in the series of compounds HX (X=H,F,Cl,Br,I) within relativistic 4-component expressions obtained by Aucar [J. Chem. Phys. 136, 204119 (2012)10.1063/1.4721627] are presented. The SR tensors of both the H and X nuclei are discussed. Calculations were carried out within the relativistic Linear Response formalism at the Random Phase Approximation with the DIRAC program. For the halogen nucleus X, correlation effects on the non-relativistic values are shown to be of similar magnitude and opposite sign to relativistic effects. For the light H nucleus, by means of the linear response within the elimination of the small component approach it is shown that the whole relativistic effect is given by the spin-orbit operator combined with the Fermi contact operator. Comparison of "best estimate" calculated values with experimental results yield differences smaller than 2-3 in all cases. The validity of "Flygares relation" linking the SR tensor and the NMR nuclear magnetic shielding tensor in the present series of compounds is analyzed. © 2013 American Institute of Physics.

Descripción: An alternative approach for the calculation of the electron-positron (e-p) contribution to magnetic properties based on two-component Breit-Pauli spinors is presented. In it, the elimination of the small component scheme is applied to the inverse propagator matrix of e-p pairs. The effect of the positronic manifold is expressed as an operator acting on Breit-Pauli spinors. The operator form thus obtained sums up the relativistic correction as a geometric series and as a result a totally different behavior in the vicinity of a nucleus is obtained as compared to the one of the linear response approximation. This feature has deep influence in numerical values of the e-p contribution to the nuclear magnetic shielding of heavy atoms. Numerical calculations carried out for Kr, Xe, and I show that with this approach, the e-p contributions to this property are in good agreement with those of four-component methods. © 2009 American Institute of Physics.

Descripción: We investigate the importance of relativistic effects on NMR shielding constants and chemical shifts of linear HgL2 (L = Cl, Br, I, CH 3) compounds using three different relativistic methods: the fully relativistic four-component approach and the two-component approximations, linear response elimination of small component (LR-ESC) and zeroth-order regular approximation (ZORA). LR-ESC reproduces successfully the four-component results for the C shielding constant in Hg(CH3)2 within 6 ppm, but fails to reproduce the Hg shielding constants and chemical shifts. The latter is mainly due to an underestimation of the change in spin-orbit contribution. Even though ZORA underestimates the absolute Hg NMR shielding constants by ∼2100 ppm, the differences between Hg chemical shift values obtained using ZORA and the four-component approach without spin-density contribution to the exchange-correlation (XC) kernel are less than 60 ppm for all compounds using three different functionals, BP86, B3LYP, and PBE0. However, larger deviations (up to 366 ppm) occur for Hg chemical shifts in HgBr 2 and HgI2 when ZORA results are compared with four-component calculations with non-collinear spin-density contribution to the XC kernel. For the ZORA calculations it is necessary to use large basis sets (QZ4P) and the TZ2P basis set may give errors of ∼500 ppm for the Hg chemical shifts, despite deceivingly good agreement with experimental data. A Gaussian nucleus model for the Coulomb potential reduces the Hg shielding constants by ∼100-500 ppm and the Hg chemical shifts by 1-143 ppm compared to the point nucleus model depending on the atomic number Z of the coordinating atom and the level of theory. The effect on the shielding constants of the lighter nuclei (C, Cl, Br, I) is, however, negligible. © 2011 American Institute of Physics.

Descripción: The noncovalent complex formed by the association of two fragments of chymotrypsin inhibitor-2 is reversibly denatured by pressure in the absence of chemical denaturants. On pressure release, the complex returned to its original conformation through a biphasic reaction, with first-order rate constants of 0.012 and 0.002 s-1, respectively. The slowest phase arises from an interconversion of the pressure-denatured state, as revealed by double pressure-jump experiments. Below 5 μM, the process was concentration dependent with a second-order rate constant of 1,700 s-1 M-1. Fragment association at atmospheric pressure showed a similar break in the order of the reaction above 5 μM, but both first- and second-order folding/association rates are 2.5 times faster than those for the refolding of the pressure-denatured state. Although the folding rates of the intact protein and the association of the fragments displayed nonlinear Eyring behavior for the temperature dependence, refolding of the pressure-denatured complex showed a linear response. The negligible heat capacity of activation reflects a balance of minimal change in the burial of residues from the pressure-denatured state to the transition state. If we add the higher energy barrier in the refolding of the pressure-denatured state, the rate differences must lie in the structure of this state, which has to undergo a structural rearrangement. This clearly differs from the conformational flexibility of the isolated fragments or the largely unfolded denatured state of the intact protein in acid and provides insight into denatured states of proteins under folding conditions.

Descripción: This study demonstrated that the λ- and ι-carrageenans, sulfated polysaccharides containing linear chains of galactopyranosyl residues, are potent inhibitors of dengue virus type 2 (DENV-2) and 3 (DENV-3) multiplication in Vero and HepG2 cells, with values of effective concentration 50% from 0.14 to 4.1 μg/ml. This activity was assayed by plaque reduction, virus yield inhibition and antigen expression tests, and was independent of the input multiplicity of infection in the range 0.001-1. The inhibitory action of the λ-carrageenan, an heparan sulfate (HS)-imitative compound, was exerted by a dual interference with virus adsorption and internalization of nucleocapsid into the cytoplasm. Although virus particles may enter the cell when compound was added after DENV-2 adsorption, as shown by intracellular uptake of radiolabeled DENV-2 particles and quantitative RT-PCR, infectious center and virion uncoating assays have shown that carrageenan-treated virions cannot be released from the endosomes. Viral protein synthesis, the first step of macromolecular synthesis after DENV entry to the host cell, was not affected by the carrageenan. Furthermore, no inhibition of virus multiplication was detected when the entry process was bypassed through DENV-2 RNA transfection into the cell. The dual sites of action of an HS-like molecule suggest that, at least in monkey kidney and human hepatic cells, the HS residues in the cell membrane appear to act as mediators for DENV-2 entry, an interesting alternative target for flavivirus therapy. © 2007 Elsevier Inc. All rights reserved.

Descripción: Imaging of samples by different microscopy techniques has produced a relevant impact in the development of new diagnosis techniques in biology, medicine and material science. In many biological, applications, where the sample changes or moves during the observation, a moving spot to track an identified sample is required. We introduce here an optical system that can perform, this tracking without mechanical components. The system, is based on the use of a high resolution liquid crystal on silicon (LCoS) device working as a mostly phase wave front modulator. The additional advantage of this system is performing the motion of the spot at video rate. In general, these devices produce coupled phase and amplitude modulation responses as a function of the applied voltage. This coupling effect deteriorates the response of those ideal optical elements designed as phase only or amplitude only functions. By means of an elliptical polarization light we can reduce the amplitude modulation and improve the phase modulation. We have experimentally found a configuration where the amplitude is almost constant while the phase reaches a high modulation. For this configuration we show how the spot can be moved through, focus plane by means of linear phases, or displaced out of this plane by using a quadratic phase. © 2008 American Institute of Physics.

Descripción: The effect of pore size to H2O2 detection by macroporous and mesoporous Prussian blue type electrocatalysts is reported in the present paper. The macroporous electrocatalysts were prepared employing spherical colloidal particles of different sizes (300, 460, 600 and 800 nm) as sacrificial templates to synthesize a copper hexacyanoferrate/polypyrrole (CuHCNFe/Ppy) hybrid material. Surprisingly, macroporous and non-porous CuHCNFe/Ppy displayed very similar results, which led to a discussion that application of macroporous platforms in sensors must consider the material wettability and the influence of electrochemical kinetics on analyte detection. In order to evaluate the effect of smaller pores, the performance of the macroporous H2O2 sensors was also compared to electrocatalysts synthesised through the immobilization of Prussian blue and CuHCNFe layers inside the cavities of mesoporous TiO2 films with diameters of 13, 20 and 40 nm. In this scale, the results were superior than those achieved with the non-porous sensors, demonstrating the possibility of controlling the performance of H2O2 sensors according to the pore diameter and the amount of immobilized material. Among the tested porous materials, the H2O2 sensor with better performance was achieved using the 20-nm diameter TiO2 platform functionalized with Prussian blue, which presented a sensitivity of (930 ± 50) μA cm-2 mmol-1 L, detection limit of (0.49 ± 0.08) μmol L-1, response time of (6 ± 2) seconds and linear range up to (1.3 ± 0.1) mmol L-1. This performance was extremely satisfactory considering sensors operating by chronoamperometry. © 2013 Elsevier Ltd. All rights reserved.

Descripción: We generalize the effective field theory of single clock inflation to include dissipative effects. Working in unitary gauge we couple a set of composite operators, OZ μ...., in the effective action which is constrained solely by invariance under time-dependent spatial diffeomorphisms. We restrict ourselves to situations where the degrees of freedom responsible for dissipation do not contribute to the density perturbations at late time. The dynamics of the perturbations is then modified by the appearance of 'friction' and noise terms, and assuming certain locality properties for the Green's functions of these composite operators, we show that there is a regime characterized by a large friction term γ H in which the ζ-correlators are dominated by the noise and the power spectrum can be significantly enhanced. We also compute the three point function hζζζi for a wide class of models and discuss under which circumstances large friction leads to an increased level of non-Gaussianities. In particular, under our assumptions, we show that strong dissipation together with the required non-linear realization of the symmetries implies |fNL| ∼ . c2s H 1. As a paradigmatic example we work out a variation of the 'trapped inflation' scenario with local response functions and perform the matching with our effective theory. A detection of the generic type of signatures that result from incorporating dissipative effects during inflation, as we describe here, would teach us about the dynamics of the early universe and also extend the parameter space of inflationary models. © SISSA 2012.

Descripción: Immune responses are qualitatively and quantitatively influenced by a complex network of receptor-ligand interactions. Among them, the CD137:CD137L pathway is known to modulate innate and adaptive human responses against Mycobacterium tuberculosis. However, the underlying mechanisms of this regulation remain unclear. In this work, we developed a Bayesian Computational Model (BCM) of in vitro CD137 signaling, devised to fit previously gathered experimental data. The BCM is fed with the data and the prior distribution of the model parameters and it returns their posterior distribution and the model evidence, which allows comparing alternative signaling mechanisms. The BCM uses a coupled system of non-linear differential equations to describe the dynamics of Antigen Presenting Cells, Natural Killer and T Cells together with the interpheron (IFN)-γ and tumor necrosis factor (TNF)-α levels in the media culture. Fast and complete mixing of the media is assumed. The prior distribution of the parameters that describe the dynamics of the immunological response was obtained from the literature and theoretical considerations Our BCM applies successively the Levenberg-Marquardt algorithm to find the maximum a posteriori likelihood (MAP); the Metropolis Markov Chain Monte Carlo method to approximate the posterior distribution of the parameters and Thermodynamic Integration to calculate the evidence of alternative hypothesis. Bayes factors provided decisive evidence favoring direct CD137 signaling on T cells. Moreover, the posterior distribution of the parameters that describe the CD137 signaling showed that the regulation of IFN-γ levels is based more on T cells survival than on direct induction. Furthermore, the mechanisms that account for the effect of CD137 signaling on TNF-α production were based on a decrease of TNF-α production by APC and, perhaps, on the increase in APC apoptosis. BCM proved to be a useful tool to gain insight on the mechanisms of CD137 signaling during human response against Mycobacterium tuberculosis. © 2013 Fernández Do Porto et al.