NMR structural study on the As-P-S glassy system

Glasses having the composition As2S3(1-x)-P2S5(x) with x ranging from 0 to 0.7 have been investigated to determine the compositional effect on properties and local structure. Glass transition temperature (T,) decreases and molar volume (V,,) increases with an increase in P content. Using P-31 NMR, we measured the strength of the P-31-P-31 magnetic dipolar interaction in the glass samples and the AsPS4 crystallized phase. Based on these data, we observed the formation of the As2P2S8 network, which reflects an increase in the average coordination number and a decrease in the degree of rigidity.

Distance determination in proteins using designed metal ion binding sites and site-directed spin labeling: application to the lactose permease of Escherichia coli.

As shown in the accompanying paper, the magnetic dipolar interaction between site-directed metal-nitroxide pairs can be exploited to measure distances in T4 lysozyme, a protein of known structure. To evaluate this potentially powerful method for general use, particularly with membrane proteins that are difficult to crystallize, both a paramagnetic metal ion binding site and a nitroxide side chain were introduced at selected positions in the lactose permease of Escherichia coli, a paradigm for polytopic membrane proteins. Thus, three individual cysteine residues were introduced into putative helix IV of a lactose permease mutant devoid of native cysteine residues containing a high-affinity divalent metal ion binding site in the form of six contiguous histidine residues in the periplasmic loop between helices III and IV. In addition, the construct contained a biotin acceptor domain in the middle cytoplasmic loop to facilitate purification. After purification and spin labeling, electron paramagnetic resonance spectra were obtained with the purified proteins in the absence and presence of Cu(II). The results demonstrate that positions 103, 111, and 121 are 8, 14, and > 23 A from the metal binding site. These data are consistent with an alpha-helical conformation of transmembrane domain IV of the permease. Application of the technique to determine helix packing in lactose permease is discussed.

Ordered magnetic dipoles: controlling anisotropy in nanomodulated continuous ferromagnetic films

In this paper, the research focus is how to entangle magnetic dipoles to control/engineer magnetic properties of different devices at a submicron/nano scale. Here, we report the generation of synthetic arrays of tunable magnetic dipoles in a nanomodulated continuous ferromagnetic film. In-plane magnetic field rotations in modulated Ni 45Fe 55 revealed various rotational symmetries of magnetic anisotropy due to dipolar interaction with a crossover from lower to higher fold as a function of modulation geometry. Additionally, the effect of aspect ratio on symmetry shows a novel phase shift of anisotropy, which could be critical to manipulate the overall magnetic properties of the patterned film. The tendency to form vortex is in fact found to be very small, which highlights that the strong coupling between metastable dipoles is more favorable than vortex formation to minimize energy in this nanomodulated structure. This has further been corroborated by the observation of step hysteresis, magnetic force microscopy images of tunable magnetic dipoles, and quantitative micromagnetic simulations. An analytical expression has been derived to estimate the overall anisotropy accurately for nanomodulated film having low magnetocrystaline anisotropy. Derived mathematical expressions based on magnetic dipolar interaction are found to be in good agreement with our results.

Dynamics of quasi-one-dimensional bright and vortex solitons of a dipolar Bose-Einstein condensate with repulsive atomic interaction

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Optical and magnetic resonance studies of the interaction of metallo tetraphenylporphyrins with nitrobenzofuroxan

Metallo tetraphenylporphyrins form I : I molecular complexes with 4,6-dinitrobenzofuroxan. The molecular association is described in terms of T-n. interaction with porphyrins functioning as donors. The association constants and thermodynamic parameters have been evaluated using optical absorption and 'H nmr spectral methods. Based on the binding constants, the donor ability of various metalloporphyrins can be arranged in the following order: Pd(I1) > Co(I1) > Cu(I1) > Ni(I1) - VO(1V) - 2H > Zn(l1). Electron paramagnetic resonance studies of the complexes reveal that the IT-complexation results in changes in the electronic structure of the central metal ions which are reflected in the changes in the M-N 5 bonding. The dipolar contribution to the acceptor proton chemical shifts in the CoTPP complex has been partitioned from ring current contributions using the shifts observed in the ZnTPP complex. The shifts, along with the line broadening ratios observed for the CoTPP complex, are used to arrive at the possible solution structures of the complexes.

Excitation and correlation of N-14 overtone transitions and measurement of heteronuclear dipolar coupling using DAPT

For studying systems containing nitrogen, limited use of N-14 NMR spectroscopy has been made because of the large quadrupolar interaction experienced by the N-14 nucleus and the absence of a central transition. To overcome the above problem, use of overtone spectroscopy has been suggested. Though this approach has limited applicability for powder samples due to second order quadrupole broadening, it is useful for studying oriented samples and single crystals. Here, we demonstrate the use of the recently proposed dipolar assisted polarization transfer (DAPT) pulse scheme for exciting the overtone transitions. The pulse sequence may also be utilized as a two-dimensional experiment to obtain H-1-N-14 dipolar couplings and H-1 chemical shifts. (C) 2010 Elsevier B.V. All rights reserved.

C-13-H-1 dipolar couplings for probing rod-like hydrogen bonded mesogens

Hydrogen bonding is the most important non-covalent interaction utilised in building supramolecular assemblies and is preferred often as a means of construction of molecular, oligomeric as well as polymeric materials that show liquid crystalline properties. In this work, a pyridine based nematogenic acceptor has been synthesized and mixed with non-mesogenic 4-methoxy benzoic acid to get a hydrogen bonded mesogen. The existence of hydrogen bonding between the pyridyl unit and the carboxylic acid was established using FT-IR spectroscopy from the observation of characteristic stretching vibrations of unionized type at 2425 and 1927 cm(-1). The mesogenic acceptor and the complex have been investigated using C-13 NMR in solution, solid and liquid crystalline states. Together with the 2D separated local field NMR experiments, the studies confirm the molecular structure in the mesophase and yield the local orientational order parameters. It is observed that the insertion of 4-methoxy benzoic acid not only enhances the mesophase stability but also induces a smectic phase due to an increase in the core length of the hydrogen bonded mesogen.

Thomas-Fermi ground state of dipolar fermions in a circular storage ring

Recent developments in the field of ultracold gases has led to the production of degenerate samples of polar molecules. These have large static electric-dipole moments, which in turn causes the molecules to interact strongly. We investigate the interaction of polar particles in waveguide geometries subject to an applied polarizing field. For circular waveguides, tilting the direction of the polarizing field creates a periodic inhomogeneity of the interparticle interaction. We explore the consequences of geometry and interaction for stability of the ground state within the Thomas-Fermi model. Certain combinations of tilt angles and interaction strengths are found to preclude the existence of a stable Thomas-Fermi ground state. The system is shown to exhibit different behavior for quasi-one-dimensional and three-dimensional trapping geometries.

Analysis of dipolar relaxation in polyurethane/polyaniline blend

Thin films of blend made up of castor oil-based polyurethane (PU) and polyaniline (PANI) were obtained by casting. The molecular mobility was studied using dielectric spectroscopy and thermally stimulated depolarization current (TSDC) for blends with two different compositions (90/10, 80/20) and the results were compared with PU pure. The peak located around -60 degrees C in TSDC thermograms of PU/PANI blend has dipolar behavior and might be attributed to the change in the molecular chain due to the interaction between isocyanate and the solvent. Vogel-Fulcher Tammann fits was performed on the observed relaxation and the result shows a alpha-relaxation-like. (c) 2005 Springer Science + Business Media, Inc.

Two-dimensional dipolar Bose-Einstein condensate bright and vortex solitons on a one-dimensional optical lattice

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Localization of a dipolar Bose-Einstein condensate in a bichromatic optical lattice

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Dipolar droplet bound in a trapped Bose-Einstein condensate

We study the statics and dynamics of a dipolar Bose-Einstein condensate (BEC) droplet bound by interspecies contact interaction in a trapped nondipolar BEC. Our findings are demonstrated in terms of stability plots of a dipolar 164Dy droplet bound in a trapped nondipolar 87Rb BEC with a variable number of 164Dy atoms and interspecies scattering length. A trapped nondipolar BEC of a fixed number of atoms can bind only a dipolar droplet containing fewer atoms than a critical number for the interspecies scattering length between two critical values. The shape and size (statics) as well as the small breathing oscillation (dynamics) of the dipolar BEC droplet are studied using numerical and variational solutions of a mean-field model. We also suggest an experimental procedure for achieving such a 164Dy droplet by relaxing the trap on the 164Dy BEC in a trapped binary 87Rb-164Dy mixture. © 2013 American Physical Society.

Bright solitons in quasi-one-dimensional dipolar condensates with spatially modulated interactions

We introduce a model for the condensate of dipolar atoms or molecules, in which the dipole-dipole interaction (DDI) is periodically modulated in space due to a periodic change of the local orientation of the permanent dipoles, imposed by the corresponding structure of an external field (the necessary field can be created, in particular, by means of magnetic lattices, which are available to the experiment). The system represents a realization of a nonlocal nonlinear lattice, which has a potential to support various spatial modes. By means of numerical methods and variational approximation (VA), we construct bright one-dimensional solitons in this system and study their stability. In most cases, the VA provides good accuracy and correctly predicts the stability by means of the Vakhitov-Kolokolov criterion. It is found that the periodic modulation may destroy some solitons, which exist in the usual setting with unmodulated DDI and can create stable solitons in other cases, not verified in the absence of modulations. Unstable solitons typically transform into persistent localized breathers. The solitons are often mobile, with inelastic collisions between them leading to oscillating localized modes. © 2013 American Physical Society.

Bright solitons in a quasi-one-dimensional dipolar Bose-Einstein condensate

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Demixing and symmetry breaking in binary dipolar Bose-Einstein-condensate solitons

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)