Ca(2.5)Sr(0.5)GaMn2O8: diamagnetic Ga in control of the structural and electronic properties of a bilayered manganate

The temperature dependence of the crystal structure and electronic properties of brownmillerite-like Ca(2.5)Sr(0.5)GaMn(2)O(8) has been studied by neutron powder diffraction and muSR spectroscopy. The results show that short-range 2D magnetic order begins to develop within the perovskite-like bilayers of MnO(6) octahedra approximately 50 K above the 3D Néel temperature of approximately 150 K. The bilayers show a structural response to the onset of magnetism throughout this temperature range whereas the GaO(4) layers that separate the bilayers only respond below the 3D ordering temperature. XANES spectroscopy shows that the sample contains Mn(3+) and Mn(4+) cations in a 1:1 ratio, and the behavior in the region of the Néel transition is interpreted as a local charge ordering. Electron diffraction and high-resolution electron microscopy have been used to show that the local microstructure is more complex than the average structure revealed by neutron diffraction, and that microdomains exist in which the GaO(4) tetrahedra show different orientations. It is argued that the bonding requirements of diamagnetic gallium control the electronic behavior within the perovskite-like bilayers.     

Practical Synthesis of (+)-Alloisoleucine

Subsequent treatment of N-crotoyl-(1S,2R)-bornane-10,2-sultam with EtMgCl, recrystallization of the product and saponification, afforded R-(-)-3-methylpenthanoic acid which was used for acylation of (1R,2S)-bornane-10,2-sultam. The product was converted into N-[(2S,3R)-2-amino-3-methylpentanoyl]-(1R,2S)-bornane-10,2-sultam by hydroxyamination with 1-chloro-1-nitrosocyclohexane, followed by reduction of the hydroxylamine grouping. Saponification of the sultam imide provided (+)-alloisoleucine.     

MR detection of mechanical vibrations using a radiofrequency field gradient

A new method for NMR characterization of mechanical waves, based upon radiofrequency field gradient for motion encoding, is proposed. A binomial B1 gradient excitation scheme was used to visualize the mobile spins undergoing a periodic transverse mechanical excitation. A simple model was designed to simulate the NMR signal as a function of the wave frequency excitation and the periodicity of the NMR pulse sequence. The preliminary results were obtained on a gel phantom at low vibration frequencies (0-200 Hz) by using a ladder-shaped coil generating a nearly constant RF field gradient along a specific known direction. For very small displacements and/or B1 gradients, the NMR signal measured on a gel phantom was proportional to the vibration amplitude and the pulse sequence was shown to be selective with respect to the vibration frequency. A good estimation of the direction of vibrations was obtained by varying the angle between the motion direction and the B1 gradient. The method and its use in parallel to more conventional MR elastography techniques are discussed. The presented approach might be of interest for noninvasive investigation of elastic properties of soft tissues and other materials.     

A method for determination of higher-order magnetic anisotropy constants — Importance of the cubic K3 and K4 for certain energy levels models

A method for determination of magnetocrystalline anisotropy constants of arbitrary order is proposed. The method is based on a least squares fitting of a phenomenological anisotropy energy for a given symmetry truncated at an arbitrary order term to a theoretical anisotropy energy computed exactly for a given energy level model. Several applications of the method to cubic systems are considered. The study reveals that the widely used expressions in the literature for the cubic constants K₁ and K₂ in terms of free energy for the three symmetry direction are of rather limitedvalidity only. The higher-order cubic constants K₃, K₄ and K₅ are determined besides the usual K₁ and K₂ in temperature range 0 to 300 K. The importance of the higher- order terms with respect to the first term in the cubic anisotropy energy is discussed. The results show that the cubic constants K₃ and K₄ cannot be neglected for most of the energy level models studied at certain temperatures.     

Detection of acoustic waves by NMR using a radiofrequency field gradient

A B(1) field gradient-based method previously described for the detection of mechanical vibrations has been applied to detect oscillatory motions in condensed matter originated from acoustic waves. A ladder-shaped coil generating a quasi-constant RF-field gradient was associated with a motion-encoding NMR sequence consisting in a repetitive binomial 13;31; RF pulse train (stroboscopic acquisition). The NMR response of a gel phantom subject to acoustic wave excitation in the 20-200 Hz range was investigated. Results showed a linear relationship between the NMR signal and the wave amplitude and a spectroscopic selectivity of the NMR sequence with respect to the input acoustic frequency. Spin displacements as short as a few tens of nanometers were able to be detected with this method.     

Mössbauer,EPR and susceptibility studies of highly conducting polypyrrole doped with iron chloride

The results of Mössbauer, EPR and static magnetic susceptibility measurements on polypyrrole doped with FeCl₃ are presented. They indicate that iron chloride tetrahedra are interacting with the polymer matrix by hydrogen bonding. This interaction increases with dehydration of the samples. The susceptibility showed a maximum near 5 K, which is an indication for antiferromagnetic interaction, probably between paramagnetic iron and polarons.     

Highly Conducting Derivatives Of Polyacetylene And Poly-Pyrrole Formed In The Reaction With Selected Protonic Acids And Metal Halides - Synthesis And Application

Abstract

It has been found that polyacetylene can be used in chemical analysis for selective determination of nitrate ion in dilute aqueous solutions. If such solutions are acidified with sulphuric acid the log σ vs. NO₃ concentration plots are linear over the NO^? ₃ concentration range 2–40 mM. Several new conducting derivatives of chemically polymerized polypyrrole have been prepared in the reaction with selected metal halides such as: FeCl₃, SbC1₅, and others. The products have been characterized by elemental analysis and conductivity measurements.     

Mass spectrometry analysis of in vitro nitration of a recombinant human IgG1 monoclonal antibody

Nitration of a recombinant human monoclonal antibody was carried out in vitro by incubating the antibody with the nitrating reagent tetranitromethane (TNM). The susceptible sites of nitration were identified using high-performance liquid chromatography/mass spectrometry (HPLC/MS). In general, tyrosine residues in the variable domains of the antibody are more susceptible to nitration, while tyrosine residues in the constant domains are relatively resistant to nitration. However, one tyrosine residue in the CH1 domain and one tyrosine residue in the CH2 domain are highly susceptible to nitration. Interestingly, the susceptible tyrosine residue in the CH2 domain is followed by the conserved asparagine residue that is glycosylated.     

Crystal field and microscopic spin Hamiltonians approach including spin-spin and spin-other-orbit interactions for d and d ions at low symmetry C3 symmetry sites: V in Al2O3

A new module has been developed within the CFA/MSH computer package, which is applicable for d² and d⁸ ions at sites of trigonal symmetry type I (C_3v,D₃,D_3d) and type II (C₃,C_3i), including the ‘imaginary’ CF term. For the first time the spin-spin (SS) and spin-other-orbit (SOO) interactions have also been included in the Hamiltonian. This module enables to study the contributions to the energy levels and the spin Hamiltonian parameters, i.e. zero-field splitting D and g-factors: g_∥ and g_⊥. The contributions arising from the spin-orbit (SO), SS, and SOO interaction as well as those due to the low symmetry CF effects induced by the distortion angle ?, which describes the difference between C₃ and C_3v symmetry, can be studied. As an application of the new module, calculations have been carried out for V³⁺(3d²) ions in α-Al₂O₃ crystal, taking into account for the first time the SS and SOO interactions, and the low symmetry CF effects. The results show that (i) the contributions from the SS and SOO interactions to the energy levels are larger for free V³⁺ ions than those for V³⁺ ions in α-Al₂O₃ crystal, (ii) both the contributions to the SH parameters and the energy levels arising from the SOO interaction are larger than those arising from the SS interaction, (iii) the contributions due to the low symmetry CF effects induced by the distortion angle ? are in general significant, (iv) D and g_⊥ are sensitive to the distortion angle ?, whereas g_∥ is insensitive to ?, and (v) the influence of the lattice distortions on the spectroscopic properties of V³⁺ ion in α-Al₂O₃ is pronounced. It appears important for similar ion-crystal cases to consider the lattice distortions in detailed calculations, which take into account the relevant contributions from the SO, SS and SOO interactions. A good agreement between the theoretical and experimental results has been obtained.