A 3D trajectory for undersampling k-space in MRSI applications

Magnetic resonance spectroscopic imaging (MRSI) is a noninvasive technique for producing spatially localized spectra. MRSI presents the important challenge of reducing the scan time while maintaining the spatial resolution. The preferred approach for this is to use time-varying readout gradients to collect the spatial and chemical-shift information. Fast, three-dimensional (3D) spatial encoded methods also reduce the scan time. Despite the existence of several new and faster 3D encoded methods, or k-space trajectories, for magnetic resonance imaging (MRI), only stack of spirals and echo planar have been studied in 3D MRSI. A novel formulation for designing fast, 3D k-space trajectory applicable to 3D MRSI is presented. This approach is simple and consists of rays expanding from the origin of k-space into a revolving sphere, collecting spectral data of all 3D spatial k-space at different times in the same scan. This article describes this new method and presents some results of its application to 3D MRSI. This technique allows some degree of undersampling; hence, it is possible to reconstruct high-quality undersampled spectroscopic imaging in order to recognize different compounds in short scan times. Additionally, the method is tested in regular 3D MRI. This proposed method can also be used for dynamic undersampled imaging.     

TeV gamma rays from photodisintegration and daughter deexcitation of cosmic-ray nuclei

It is commonly assumed that high-energy gamma rays are made via either purely electromagnetic processes or the hadronic process of pion production, followed by decay. We investigate astrophysical contexts where a third process (A*) would dominate: namely, the photodisintegration of highly boosted nuclei followed by daughter deexcitation. Starburst regions such as Cygnus OB2 appear to be promising sites for TeV gamma-ray emission via this mechanism. A unique feature of the A* process is a sharp flattening of the energy spectrum below approximately 10 TeV/(T/eV) for gamma-ray emission from a thermal region of temperature T. The A* mechanism described herein offers an important contribution to gamma-ray astronomy in the era of intense observational activity.     

Coexistence of ordinary elasticity and superfluidity in a model of a defect-free supersolid

The mechanical behavior of a supersolid is studied in the framework of a fully explicit model derived from the Gross-Pitaevskii equation without assuming any defect or vacancy. A set of coupled nonlinear partial differential equations plus boundary conditions is derived. The conditions of mechanical equilibrium are studied under external constraints such as steady rotation and external stress. Our model explains the experimentally observed paradoxical behavior: a nonclassical rotational inertia fraction in the limit of small rotation speed but a solidlike elastic response to small stress or an external force field.     

One-dimensional phosphinite platinum chains based on hydrogen bonding interactions and phosphinite tetranuclear platinum(II)-thallium(I) complexes

The mononuclear pentafluorophenyl platinum complex containing the chelated diphenylphosphinous acid/diphenylphosphinite system [Pt(C(6)F(5)){(PPh(2)O)(2)H}(PPh(2)OH)] 1 has been prepared and characterised. 1 and the related alkynyl complex [Pt(C[triple bond, length as m-dash]CBu(t)){(PPh(2)O)(2)H}(PPh(2)OH)] 2 form infinite one-dimensional chains in the solid state based on intermolecular O-H[dot dot dot]O hydrogen bonding interactions. Deprotonation reactions of [PtL{(PPh(2)O)(2)H}(PPh(2)OH)] (L = C(6)F(5), C[triple bond, length as m-dash]CBu(t), C[triple bond, length as m-dash]CPh 3) with [Tl(acac)] yields tetranuclear Pt(2)Tl(2) complexes [PtL{(PPh(2)O)(2)H}(PPh(2)O)Tl](2) (L = C(6)F(5) 4, C[triple bond, length as m-dash]CBu(t), C[triple bond, length as m-dash]CPh ). The structure of the tert-butylalkynyl derivative , established by X-ray diffraction, shows two anionic discrete units [Pt(C[triple bond, length as m-dash]CBu(t)){(PPh(2)O)(2)H}(PPh(2)O)](-) joined by two Tl(i) centres via Tl-O and Pt-Tl bonds. Despite the existence of Pt-Tl interactions, they do not show luminescence.     

Liquid-structure forces and electrostatic modulation of biomolecular interactions in solution

Molecular interactions in solution are controlled by the bulk medium and by the forces originating in the structured region of the solvent close to the solutes. In this paper, a model of electrostatic and liquid-structure forces for dynamics simulations of biomolecules is presented. The model introduces information on the microscopic nature of the liquid in the vicinity of polar and charged groups and the associated non-pairwise character of the forces, thus improving upon conventional continuum representations. The solvent is treated as a polar and polarizable medium, with dielectric properties described by an inhomogeneous version of the Onsager theory. This treatment leads to an effective position-dependent dielectric permittivity that incorporates saturation effects of the electric field and the spatial variation of the liquid density. The non-pairwise additivity of the liquid-structure forces is represented by centers of force located at specific points in the liquid phase. These out-of-the-solute centers are positioned at the peaks of liquid density and exert local, external forces on the atoms of the solute. The density is calculated from a barometric law, using a Lennard-Jones-type solute-liquid effective interaction potential. The conceptual aspects of the model and its exact numerical solutions are discussed for single alkali and halide ions and for ion-pair interactions. The practical aspects of the model and the simplifications introduced for efficient computation of forces in molecular solutes are discussed in the context of polar and charged amino acid dimers. The model reproduces the contact and solvent-separated minima and the desolvation barriers of intermolecular potentials of mean force of amino acid dimers, as observed in atomistic dynamics simulations. Possible refinements based on an improved treatment of molecular correlations are discussed.     

Computer simulation of the interaction of Cu(I) with cys residues at the binding site of the yeast metallochaperone Cu(I)-Atx1

The copper binding site and electronic structure of the metallochaperone protein Atx1 were investigated using the combination of quantum mechanics methods and molecular mechanics methods in the ONIOM(QM:MM) scheme at the density functional theory (DFT) B3LYP/ 6-31G(d):AMBER level. The residues in the binding site, -Met13-Thr14-Cys15-Cu(I)-Cys18-Gly17-Ser16-, were modeled with QM and the rest of the residues with MM. Our results indicate that the structure for Cu(I)-Atx1 has the copper atom coordinated to two sulfur atoms from Cys15 (2.110 A) and Cys18 (2.141 A) with an angle S-Cu(I) -S of 166 degrees . The potential energy surface of the copper atom is used to estimate its binding energy and the force field for the copper ligands. The potential surface is shallow for the bending mode S-Cu-S, which explains the origin of the disorder observed in crystallographic and nuclear magnetic resonance studies. Using molecular dynamics for Cu(I)-Atx1 in a box of water molecules and in vacuum, with the force field derived in this work, we observed a correlated motion between the side chains of Thr14 and of Lys65 which enhances distortions in the S-Cu-S geometry. The results are compared with recent experiments and the previous models. The vibrational spectra for the copper ligands and for the residues in the binding site were computed. The localized modes for the copper ligands and the amide bands were assigned. The presence of the copper atom affects the amide bands' frequencies of the residues Cys15 and Cys18, giving resolved bands that can be used to sense changes in the binding site upon translocation of copper atom or interaction with target proteins. Furthermore, the EXAFS (extended X-ray absorption fine structure) spectrum of the proposed structure for Cu(I)-Atx1 was calculated and reproduced the experiments fairly well.     

Enantiopure vs. racemic metalloligands: impact on metal-organic framework structure and synthesis

Carboxylate-decorated tris(dipyrrinato) cobalt(III) complexes have been used to construct 2-D and 3-D metal-organic frameworks with infinite and trinuclear zinc secondary-building units.     

Characterization of trimetallic Pt-Pd-Au/CeO2 catalysts combinatorial designed for methane total oxidation

In the present work, the role and the effect of platinum and gold on the catalytic performance of ceria supported tri-metallic Pt-Pd-Au catalysts have been studied. The optimum composition of these tri-metallic supported catalysts has been discovered using methods and tools of combinatorial catalyst library design. Detailed catalytic, spectroscopic and physico-chemical characterization of catalysts in the vicinity of the optimum in the given compositional space has been performed. The temperature-programmed oxidation of methane revealed that the addition of Pt and Au to Pd/CeO2 catalyst resulted in higher conversion values in the whole investigated temperature range compared to the monometallic Pd catalyst. The time-on-stream experiments provided further evidence for the high-stability of tri-metallic catalysts compared to the monometallic one. Kinetic studies revealed the stronger adsorption of methane on Pt-Pd/CeO2 catalysts than over Pd/CeO2. XPS analysis showed that Pt and Au stabilize Pd in a more reduced form even under condition of methane oxidation. FTIR spectroscopy of adsorbed CO and hydrogen TPD measurements provided indirect evidences for alloying of Pt and Au with Pd. CO chemisorption data indicated that tri-metallic catalysts have increased accessible metallic surface area. It is suggested that advantageous catalytic properties of tri-metallic Pt-Au-Pd/CeO2 catalysts compared to the monometallic one can be attributed to (i) suppression of the formation of ionic forms of Pd(II), (ii) reaching an optimum ratio between Pd0 and PdO species, and (iii) stabilization of Pd in high dispersion. The results also indicate that Pd0 - PdO ensemble sites are required for methane activation.     

On the Spectrum of an Hamiltonian in Fock Space. Discrete Spectrum Asymptotics

A model operator H associated with the energy operator of a system describing three particles in interaction, without conservation of the number of particles, is considered. The location of the essential spectrum of H is described. The existence of infinitely many eigenvalues (resp. the finiteness of eigenvalues) below the bottom τ_ess(H) of the essential spectrum of H is proved for the case where the associated Friedrichs model has a threshold energy resonance (resp. a threshold eigenvalue). For the number N(z) of eigenvalues of H lying below z < τ_ess(H) the following asymptotics is found

Spectral Characterization of Thiophene Acylhydrazides

The spectroscopic properties of a series of new thiophene acylhydrazides were examined. Extremely low fluorescence quantum yields were observed for all these compounds including the hydrazide parent compound and their acylhydrazide homologous polymers. The heteroatoms concomitant with the thiophene sulfurs were responsible for decreasing the singlet-triplet energy level resulting in increased intersystem crossing and low fluorescence emission for the studied compounds. Intramolecular triplet self-quenching from the acylhydrazide bond ultimately deactivates the triplet state by non-emissive means.