Photoluminescence study of new lanthanide complexes with benzeneseleninic acids

New lanthanide complexes with benzeneseleninic (ABSe) and 4-chloro-benzeneseleninic (ABSeCl) acids have been synthesized and characterized by elemental analysis, infrared and UV-visible spectroscopies. The emission spectra of the trivalent europium complexes presented the typical electronic (5)D(0) -> (7)F(j) transitions of the ion (J = 0-4). The ground-state geometries of the europium complexes have been calculated by using the Sparkle/AM1 model. From these results, the 4f-4f intensity parameters and energies of the ligand singlet and triplet excited states have been obtained. The lower emission quantum yield for the [Eu(ABSe)(3)(H(2)O)(2)](H(2)O)(2) compound, as compared to the [Eu(Al(3)SeCl)(3)(H(2)O)(2)] one, can be associated to the higher numbers of water molecules, in the first and second coordination spheres, that contribute to the luminescence quenching. The [Eu(Al(3)Se)(3)(H(2)O)(2)](H(2)O)(2) complex presents an intermediate state whose energy difference with respect to the first excited singlet state is resonant with three phonons from the water molecules, favouring a multiphonon relaxation process from the singlet state followed by a fast internal conversion process; this effect is less pronounced in the complex with the ABSeCl ligand. The luminescence decay curves of the gadolinium complexes indicate that the level responsible for the intramolecular energy transfer process has a triplet character for both compounds. The nephelauxetic effect in these compounds was investigated under the light of a recently proposed covalency scale based on the concept of overlap polarizability of the chemical bond. (C) 2009 Elsevier B.V. All rights reserved.

Four-level systems and a universal quantum gate

We discuss the possibility of implementing a universal quantum XOR gate by using two coupled quantum dots subject to external magnetic fields that are parallel and slightly different. We consider this system in two different field configurations. In the first case, parallel external fields with the intensity difference at each spin being proportional to the time-dependent interaction between the spins. A general exact solution describing this system is presented and analyzed to adjust field parameters. Then we consider parallel fields with intensity difference at each spin being constant and the interaction between the spins switching on and off adiabatically. In both cases we adjust characteristics of the external fields (their intensities and duration) in order to have the parallel pulse adequate for constructing the XOR gate. In order to provide a complete theoretical description of all the cases, we derive relations between the spin interaction, the inter-dot distance, and the external field. (C) 2008 WILEYNCH Verlag GmbH & Co. KGaA. Weinheim.

WRITING ELECTRONIC FERROMAGNETIC STATES IN A HIGH-TEMPERATURE PARAMAGNETIC NUCLEAR SPIN SYSTEM

In this paper, we use Nuclear Magnetic Resonance (NMR) to write electronic states of a ferromagnetic system into high-temperature paramagnetic nuclear spins. Through the control of phase and duration of radio frequency pulses, we set the NMR density matrix populations, and apply the technique of quantum state tomography to experimentally obtain the matrix elements of the system, from which we calculate the temperature dependence of magnetization for different magnetic fields. The effects of the variation of temperature and magnetic field over the populations can be mapped in the angles of spin rotations, carried out by the RF pulses. The experimental results are compared to the Brillouin functions of ferromagnetic ordered systems in the mean field approximation for two cases: the mean field is given by (i) B = B(0) + lambda M and (ii) B = B(0) + lambda M + lambda`M(3), where B(0) is the external magnetic field, and lambda, lambda` are mean field parameters. The first case exhibits second order transition, whereas the second case has first order transition with temperature hysteresis. The NMR simulations are in good agreement with the magnetic predictions.

CMB and LSS constraints on a single-field model of inflation

A new inflationary scenario whose exponential potential V (Phi) has a quadratic dependence on the field Phi in addition to the standard linear term is confronted with the five-year observations of the Wilkinson-Microwave Anisotropy Probe and the Sloan Digital Sky Survey data. The number of e-folds (N), the ratio of tensor-to-scalar perturbations (r), the spectral scalar index of the primordial power spectrum (n(s)) and its running (dn(s)/d ln k) depend on the dimensionless parameter a multiplying the quadratic term in the potential. In the limit a. 0 all the results of the exponential potential are fully recovered. For values of alpha not equal 0, we find that the model predictions are in good agreement with the current observations of the Cosmic Microwave Background (CMB) anisotropies and Large-Scale Structure (LSS) in the Universe. Copyright (C) EPLA, 2008.

COMPARISONS OF THE INTERSTELLAR MAGNETIC FIELD DIRECTIONS OBTAINED FROM THE IBEX RIBBON AND INTERSTELLAR POLARIZATIONS

Variations in the spatial configuration of the interstellar magnetic field (ISMF) near the Sun can be constrained by comparing the ISMF direction at the heliosphere found from the Interstellar Boundary Explorer (IBEX) spacecraft observations of a ""Ribbon"" of energetic neutral atoms (ENAs), with the ISMF direction derived from optical polarization data for stars within similar to 40 pc. Using interstellar polarization observations toward similar to 30 nearby stars within similar to 90 degrees of the heliosphere nose, we find that the best fits to the polarization position angles are obtained for a magnetic pole directed toward ecliptic coordinates of lambda, beta similar to 263 degrees, 37 degrees (or galactic coordinates of l, b similar to 38 degrees, 23 degrees), with uncertainties of +/- 35 degrees based on the broad minimum of the best fits and the range of data quality. This magnetic pole is 33 degrees from the magnetic pole that is defined by the center of the arc of the ENA Ribbon. The IBEX ENA ribbon is seen in sight lines that are perpendicular to the ISMF as it drapes over the heliosphere. The similarity of the polarization and Ribbon directions for the local ISMF suggests that the local field is coherent over scale sizes of tens of parsecs. The ISMF vector direction is nearly perpendicular to the flow of local interstellar material (ISM) through the local standard of rest, supporting a possible local ISM origin related to an evolved expanding magnetized shell. The local ISMF direction is found to have a curious geometry with respect to the cosmic microwave background dipole moment.

Suppression of small baryonic structures due to a primordial magnetic field

We investigate the impact of the existence of a primordial magnetic field on the filter mass, characterizing the minimum baryonic mass that can form in dark matter (DM) haloes. For masses below the filter mass, the baryon content of DM haloes are severely depressed. The filter mass is the mass when the baryon to DM mass ratio in a halo is equal to half the baryon to DM ratio of the Universe. The filter mass has previously been used in semi-analytic calculations of galaxy formation, without taking into account the possible existence of a primordial magnetic field. We examine here its effect on the filter mass. For homogeneous comoving primordial magnetic fields of B(0) similar to 1 or 2 nG and a re-ionization epoch that starts at a redshift z(s) = 11 and is completed at z(r) = 8, the filter mass is increased at redshift 8, for example, by factors of 4.1 and 19.8, respectively. The dependence of the filter mass on the parameters describing the re-ionization epoch is investigated. Our results are particularly important for the formation of low-mass galaxies in the presence of a homogeneous primordial magnetic field. For example, for B(0) similar to 1 nG and a re-ionization epoch of z(s) similar to 11 and z(r) similar to 7, our results indicate that galaxies of total mass M similar to 5 x 108 M(circle dot) need to form at redshifts z(F) greater than or similar to 2.0, and galaxies of total mass M similar to 108 M(circle dot) at redshifts z(F) greater than or similar to 7.7.

SIMULATIONS OF WINDS OF WEAK-LINED T TAURI STARS: THE MAGNETIC FIELD GEOMETRY AND THE INFLUENCE OF THE WIND ON GIANT PLANET MIGRATION

By means of numerical simulations, we investigate magnetized stellar winds of pre-main-sequence stars. In particular, we analyze under which circumstances these stars will present elongated magnetic features (e.g., helmet streamers, slingshot prominences, etc). We focus on weak-lined T Tauri stars, as the presence of the tenuous accretion disk is not expected to have strong influence on the structure of the stellar wind. We show that the plasma-beta parameter (the ratio of thermal to magnetic energy densities) is a decisive factor in defining the magnetic configuration of the stellar wind. Using initial parameters within the observed range for these stars, we show that the coronal magnetic field configuration can vary between a dipole-like configuration and a configuration with strong collimated polar lines and closed streamers at the equator (multicomponent configuration for the magnetic field). We show that elongated magnetic features will only be present if the plasma-beta parameter at the coronal base is beta(0) << 1. Using our self-consistent three-dimensional magnetohydrodynamics model, we estimate for these stellar winds the timescale of planet migration due to drag forces exerted by the stellar wind on a hot-Jupiter. In contrast to the findings of Lovelace et al., who estimated such timescales using the Weber and Davis model, our model suggests that the stellar wind of these multicomponent coronae are not expected to have significant influence on hot-Jupiters migration. Further simulations are necessary to investigate this result under more intense surface magnetic field strengths (similar to 2-3 kG) and higher coronal base densities, as well as in a tilted stellar magnetosphere.

A statistical evaluation of the field emission for copper oxide nanostructures

A statistical data analysis methodology was developed to evaluate the field emission properties of many samples of copper oxide nanostructured field emitters. This analysis was largely done in terms of Seppen-Katamuki (SK) charts, field strength and emission current. Some physical and mathematical models were derived to describe the effect of small electric field perturbations in the Fowler-Nordheim (F-N) equation, and then to explain the trend of the data represented in the SK charts. The field enhancement factor and the emission area parameters showed to be very sensitive to variations in the electric field for most of the samples. We have found that the anode-cathode distance is critical in the field emission characterization of samples having a non-rigid nanostructure. (C) 2007 Elsevier B.V. All rights reserved.

Coherent and semiclassical states in a magnetic field in the presence of the Aharonov-Bohm solenoid

A new approach to constructing coherent states (CS) and semiclassical states (SS) in a magnetic-solenoid field is proposed. The main idea is based on the fact that the AB solenoid breaks the translational symmetry in the xy-plane; this has a topological effect such that there appear two types of trajectories which embrace and do not embrace the solenoid. Due to this fact, one has to construct two different kinds of CS/SS which correspond to such trajectories in the semiclassical limit. Following this idea, we construct CS in two steps, first the instantaneous CS (ICS) and then the time-dependent CS/SS as an evolution of the ICS. The construction is realized for nonrelativistic and relativistic spinning particles both in (2 + 1) and (3 + 1) dimensions and gives a non-trivial example of SS/CS for systems with a nonquadratic Hamiltonian. It is stressed that CS depending on their parameters (quantum numbers) describe both pure quantum and semiclassical states. An analysis is represented that classifies parameters of the CS in such respect. Such a classification is used for the semiclassical decompositions of various physical quantities.

A dedicated setup for the measurement of the electron transport parameters in gases at large electric fields

Electron transport parameters are important in several areas ranging from particle detectors to plasma-assisted processing reactors. Nevertheless, especially at high fields strengths and for complex gases, relatively few data are published. A dedicated setup has been developed to measure the electron drift velocity and the first Townsend coefficient in parallel plate geometry. An RPC-like cell has been adopted to reach high field strengths without the risk of destructive sparks. The validation data obtained with pure Nitrogen will be presented and compared to a selection of the available literature and to calculations performed with Magboltz 2 version 8.6. The new data collected in pure Isobutane will then be discussed. This is the first time the electron drift velocity in pure Isobutane is measured well into the saturation region. Good agreement is found with expectations from Magboltz. (C) 2009 Elsevier B.V. All rights reserved.

Synthesis and Crystal Structures of Octahedral Sn(IV) Complexes Prepared from SnCl(2)center dot 2H(2)O and 2-Hydroxyacetophenone (S-benzydithiocarbazate) Ligand (H(2)L)

Two coordination octahedral Sn(IV) complexes [Sn(L)(2)] and cis-[SnCl(2)(L)(dmso)], where H(2)L is 2-hydroxyacetophenone (S-benzydithiocarbazate), were prepared and characterized by elemental analysis, IR, NMR ((1)H, (13)C), (119)Sn Mossbauer spectroscopies and X-ray diffraction techniques to investigate their structural properties. Both crystallize in the Monoclinic system, with parameters: a = 8.1905(3), b = 30.8811(15), c = 12.8959(7) angstrom, beta = 94.465(3)degrees and Z = 4 for [Sn(L)(2)] and a = 8.5247(2), b = 21.5445(7), c = 12.3706(3) angstrom, beta = 96.932(2)degrees and Z = 4 for cis-[SnCl(2)(L)(dmso)]. In both complexes, the Sn(IV) central atom is coordinated in a distorted octahedral geometry with the thiolate ligand (L(2-)) coordinated via O, N and S atoms. The (119)Sn Mossbauer spectroscopy of the complexes were studied and the results revealed that both complexes posses isomer shift (delta) and quadrupole splitting (Delta), which are almost the same.

Ligand induced interaction of thyroid hormone receptor beta with its coregulators

Thyroid hormones exert most of their physiological effects through two thyroid hormone receptor (TR) subtypes, TR alpha and TR beta, which associate with many transcriptional coregulators to mediate activation or repression of target genes. The search for selective TR beta ligands has been stimulated by the finding that several pharmacological actions mediated by TR beta might be beneficial in medical conditions such as obesity, hypercholesterolemia and diabetes. Here, we present a new methodology which employs surface plasmon resonance to investigate the interactions between TR beta ligand binding domain (LBD) complexes and peptides derived from the nuclear receptor interaction motifs of two of its coregulators, SRC2 and DAX1. The effect of several TR beta ligands, including the TR beta selective agonist GC-I and the TR beta selective antagonist NH-3, were investigated. We also determined the kinetic rate constants for the interaction of TR beta-T3 with both coregulators, and accessed the thermodynamic parameters for the interaction with DAX1. Our findings Suggest that flexibility plays an important role in the interaction between the receptor and its coregulators. and point out important aspects of experimental design that should be addressed when using TR beta LBD and its agonists. Furthermore, the methodology described here may be useful for the identification of new TR beta ligands. (C) 2008 Elsevier Ltd. All rights reserved.

Ligand dissociation from estrogen receptor is mediated by receptor dimerization: Evidence from molecular dynamics simulations

Estrogen Receptor (ER) is an important target for pharmaceutical design. Like other ligand-dependent transcription factors, hormone binding regulates ER transcriptional activity. Nevertheless, the mechanisms by which ligands enter and leave ERs and other nuclear receptors remain poorly understood. Here, we report results of locally enhanced sampling molecular dynamics simulations to identify dissociation pathways of two ER ligands [the natural hormone 17 beta-estradiol (E-2) and the selective ER modulator raloxifene (RAL)] from the human ER alpha ligand-binding domain in monomeric and dimeric forms. E-2 dissociation occurs via three different pathways in ER monomers. One resembles the mousetrap mechanism (Path I), involving repositioning of helix 12 (H12), others involve the separation of H8 and H11 (Path II), and a variant of this pathway at the bottom of the ligand-binding domain (Path II`). RAL leaves the receptor through Path I and a Path I variant in which the ligand leaves the receptor through the loop region between H11 and H12 (Path I`). Remarkably, ER dimerization strongly suppresses Paths II and II` for E-2 dissociation and modifies RAL escape routes. We propose that differences in ligand release pathways detected in the simulations for ER monomers and dimers provide an explanation for previously observed effects of ER quaternary state on ligand dissociation rates and suggest that dimerization may play an important, and hitherto unexpected, role in regulation of ligand dissociation rates throughout the nuclear receptor family.

Axial ligand influence on geometries, charge distributions and electronic structures of iron tetraazamacrocycle [Fe((II))TIM(X)(Y)](2+) complexes assessed by Density Functional Theory

We employed the Density Functional Theory along with small basis sets, B3LYP/LANL2DZ, for the study of FeTIM complexes with different pairs of axial ligands (CO, H(2)O, NH(3), imidazole and CH(3)CN). These calculations did not result in relevant changes of molecular quantities as bond lengths, vibrational frequencies and electronic populations supporting any significant back-donation to the carbonyl or acetonitrile axial ligands. Moreover, a back-donation mechanism to the macrocycle cannot be used to explain the observed changes in molecular properties along these complexes with CO or CH(3)CN. This work also indicates that complexes with CO show smaller binding energies and are less stable than complexes with CH(3)CN. Further, the electronic band with the largest intensity in the visible region (or close to this region) is associated to the transition from an occupied 3d orbital on iron to an empty pi* orbital located at the macrocycle. The energy of this Metal-to-Ligand Charge Transfer (MLCT) transition shows a linear relation to the total charge of the macrocycle in these complexes as given by Mulliken or Natural Population Analysis (NPA) formalisms. Finally, the macrocycle total charge seems to be influenced by the field induced by the axial ligands. (C) 2011 Elsevier Ltd. All rights reserved.