Random existence of charge ordered stripes and its influence on the magnetotransport properties of La0.6Sr0.4MnO3 perovskite substituted with diamagnetic ions at Mn sublattice

Phase-singular solid solutions of La0.6Sr0.4Mn1-yMeyO3 (0 <= y <= 0.3) [Me=Li1+, Mg2+, Al3+, Ti4+, Nb5+, Mo6+ or W6+] [LSMey] perovskite of rhombohedral symmetry (space group: R (3) over barc) have been prepared wherein the valence of the diamagnetic substituent at Mn site ranged from 1 to 6. With increasing y-content in LSMey, the metal-insulator (TM-I) transition in resistivity-temperature rho(T) curves shifted to low temperatures. The magnetization studies M(H) as well as the M(T) indicated two groups for LSMey. (1) Group A with Me=Mg, Al, Ti, or Nb which are paramagnetic insulators (PIs) at room temperature with low values of M (< 0.5 mu(B)/Mn); the magnetic transition [ferromagnetic insulator (FMI)-PI] temperature (T-C) shifts to low temperatures and nearly coincides with that of TM-I and the maximum magnetoresistance (MR) of similar to 50% prevails near T-C (approximate to TM-I). (2) Group-B samples with Me=Li, Mo, or W which are FMIs with M-s=3.3-3.58 mu(B)/Mn and marginal reduction in T-C similar to 350 K as compared to the undoped LSMO (T-C similar to 378 K). The latter samples show large temperature differences Delta T=T-c-TM-I, reaching up to similar to 288 K. The maximum MR (similar to 60%) prevails at low temperatures corresponding to the M-I transition TM-I rather than around T-C. High resolution lattice images as well as microscopy analysis revealed the prevalence of inhomogeneous phase mixtures of randomly distributed charge ordered-insulating (COI) bistripes (similar to 3-5 nm width) within FMI charge-disordered regions, yet maintaining crystallographically single phase with no secondary precipitate formation. The averaged ionic radius < r(B)>, valency, or charge/radius ratio < CRR > cannot be correlated with that of large Delta T; hence cannot be used to parametrize the discrepancy between T-C and TM-I. The M-I transition is controlled by the charge conduction within the electronically heterogeneous mixtures (COI bistripes+FMI charge disordered); large MR at TM-I suggests that the spin-ordered FM-insulating regions assist the charge transport, whereas the T-C is associated with the bulk spin ordered regions corresponding to the FMI phase of higher volume fraction of which anchors the T-C to higher temperatures. The present analysis showed that the double-exchange model alone cannot account for the wide bifurcation of the magnetic and electric transitions, contributions from the charge as well as lattice degrees of freedom to be separated from spin/orbital ordering. The heterogeneous phase mixtures (COI+FMI) cannot be treated as of granular composite behavior. (c) 2008 American Institute of Physics.

Unlocking the potential of bile acids in synthesis, supramolecular/materials chemistry and nanoscience

The Maitra group has explored a variety of chemistry with bile acids during the past 15 years and these experiments have covered a wide variety of chemistry - asymmetric synthesis, molecular recognition, ion receptors/sensors, dendrimers, low molecular mass organo and hydrogelators, gel-nanoparticle composites, etc. Some of what excites us in this field is highlighted in this perspective article.

Structural Ordering of Disordered Ligand-Binding Loops of Biotin Protein Ligase into Active Conformations as a Consequence of Dehydration

Mycobacterium tuberculosis (Mtb), a dreaded pathogen, has a unique cell envelope composed of high fatty acid content that plays a crucial role in its pathogenesis. Acetyl Coenzyme A Carboxylase (ACC), an important enzyme that catalyzes the first reaction of fatty acid biosynthesis, is biotinylated by biotin acetyl-CoA carboxylase ligase (BirA). The ligand-binding loops in all known apo BirAs to date are disordered and attain an ordered structure only after undergoing a conformational change upon ligand-binding. Here, we report that dehydration of Mtb-BirA crystals traps both the apo and active conformations in its asymmetric unit, and for the first time provides structural evidence of such transformation. Recombinant Mtb-BirA was crystallized at room temperature, and diffraction data was collected at 295 K as well as at 120 K. Transfer of crystals to paraffin and paratone-N oil (cryoprotectants) prior to flash-freezing induced lattice shrinkage and enhancement in the resolution of the X-ray diffraction data. Intriguingly, the crystal lattice rearrangement due to shrinkage in the dehydrated Mtb-BirA crystals ensued structural order of otherwise flexible ligand-binding loops L4 and L8 in apo BirA. In addition, crystal dehydration resulted in a shift of similar to 3.5 angstrom in the flexible loop L6, a proline-rich loop unique to Mtb complex as well as around the L11 region. The shift in loop L11 in the C-terminal domain on dehydration emulates the action responsible for the complex formation with its protein ligand biotin carboxyl carrier protein (BCCP) domain of ACCA3. This is contrary to the involvement of loop L14 observed in Pyrococcus horikoshii BirA-BCCP complex. Another interesting feature that emerges from this dehydrated structure is that the two subunits A and B, though related by a noncrystallographic twofold symmetry, assemble into an asymmetric dimer representing the ligand-bound and ligand-free states of the protein, respectively. In-depth analyses of the sequence and the structure also provide answers to the reported lower affinities of Mtb-BirA toward ATP and biotin substrates. This dehydrated crystal structure not only provides key leads to the understanding of the structure/function relationships in the protein in the absence of any ligand-bound structure, but also demonstrates the merit of dehydration of crystals as an inimitable technique to have a glance at proteins in action.

Unusual dielectric response in B-site size-disordered hexagonal transition metal oxides

We discover that hexagonal holmium copper titanate (Ho2CuTiO6), has a unique and highly desirable combination of high dielectric constant, low losses, very small temperature coefficient, and low frequency dependence. Our first-principles calculations indicate that these exceptional properties result from a size-difference at the Cu/Ti B-site that suppresses the expected ferroelectric transition, combined with the dominance of intermediate-frequency polar vibrational modes in the dielectric response. Our results suggest that the use of such B-site disorder in alloys of hexagonal transition-metal oxides should generally result in similar robust dielectrics.

Influence of External Light Waves on the Thermoelectric Power Under Strong Magnetic Field in Ultrathin Films, Quantum Wires and Quantum Dots of Optoelectronic Materials

In this paper, an attempt is made to study the influence of external light waves on the thermoelectric power under strong magnetic field (TPSM) in ultrathin films (UFs), quantum wires (QWs) and quantum dots (QDs) of optoelectronic materials whose unperturbed dispersion relation of the conduction electrons are defined by three and two band models of Kane together with parabolic energy bands on the basis of newly formulated electron dispersion laws in each case. We have plotted the TPSM as functions of film thickness, electron concentration, light intensity and wavelength for UFs, QWs and ODs of InSb, GaAs, Hg1-xCdxTe and In1-xGaxAsyP1-y respectively. It appears from the figures that for UFs, the TPSM increases with increasing thickness in quantum steps, decreases with increasing electron degeneracy exhibiting entirely different types of oscillations and changes with both light intensity and wavelength and these two latter types of plots are the direct signature of light waves on opto-TPSM. For QWs, the opto-TPSM exhibits rectangular oscillations with increasing thickness and shows enhanced spiky oscillations with electron concentration per unit length. For QDs, the opto-TPSM increases with increasing film thickness exhibiting trapezoidal variations which occurs during quantum jumps and the length and breadth of the trapezoids are totally dependent on energy band constants. Under the condition of non-degeneracy, the results of opto-TPSM gets simplified into the well-known form of classical TPSM equation which the function of three constants only and being invariant of the signature of band structure.

On the theory of the indentation test for the measurement of tensile strength of brittle materials

A theoretical solution has been obtained for the state of stress in a rectangular plate under a pair of symmetrically placed rigid indenters. The stress distributions along the two central axes have been calculated for a square plate assuming the pressure distribution under the indenters as uniform, parabolic and one resulting from 'constant displacement' on a semiinfinite boundary, for different ratios of indenter-width to side of square. The results are compared with those of photoelastic analysis of Berenbaum and Brodie and the validity of the solution is discussed. The solution has been extended to orthotropic materials and numerical results for one type of coal are given.

Structure and electron transport anomalies in InSe-In6Se 7 composite

Rapid solidification of an equiatomic In-Se alloy resulted in the formation of an equilibrium InSe-In6Se7 phase mixture. The InSe phase was found to be polytypic and exhibited the structural variants 2H, 3H, and 4H. The 4H polytype was found to be in considerably higher proportion compared to 2H and 3H types. The In6Se7 phase was found to be hexagonal with a=0.8919 nm and c=1.4273 nm. Both In6Se 7 and the polytypes of InSe could be identified with the space group P61. The conductivity σ variation with temperature was found to be similar to that observed in disordered semiconducting materials. For temperatures >200 K, ln σ decreased linearly with T-1, phonon-assisted carrier excitation. For temperatures <200 K, ln σ decrease followed T-1/3 behavior, representative of variable-range hopping conduction of electrons.

Phase diagram and dielectric studies of binary organic materials

The phase equilibrium studies of organic system, involving resorcinol (R) and p-dimethylaminobenzaldehyde (DMAB), reveal the formation of a 1:1 molecular complex with two eutectics. The heat of mixing, entropy of fusion, roughness parameter, interfacial energy, and the excess thermodynamic functions were calculated based on enthalpy of fusion data determined via differential scanning calorimetric (DSC) method. X-ray powder diffraction studies confirm that the eutectics are not simple mechanical mixture of the components under investigation. The spectroscopic investigations (IR and NMR) suggest the occurrence of hydrogen bonding between the components forming the molecular complex. The dielectric measurements, carried out on hot-pressed addition compound (molecular complex), show higher dielectric constant at 320 K than that of individual components. The microstructural investigations of eutectic and addition compound indicate dendritic and faceted morphological features. (C) 2000 Elsevier Science B.V. All rights reserved.

Ba3ZnTa2-xNbxO9 and Ba3MgT2-xNbxO9: synthesis, structural and dielectric studies

Oxides of the families Ba3ZnTa2-xNbxO9 and Ba3MgTa2-xNbxO9 were obtained by the solid state reaction route at 1573 K and were found to crystallize in the disordered (cubic) perovskite structure. In Ba3ZnTa2-xNbXO9 and Ba3MgTa2-xNbxO9 the entire range (0 less than or equal to x less than or equal to 1) of solid solutions could be synthesized. The dielectric constant decreases with increase in frequency for all compositions in the range 40 Hz to 100 kHz (epsilon (r) varies from 16 to 22). The dielectric loss (D) shows a broad maximum for both Ba3ZnTa2-xNbxO9 and Ba3MgTa2-xNbxO9. The maxima is centered around 2 kHz in the former and near 10 kHz in the latter. (C) 2001 Elsevier Science Ltd. All sights reserved.

Energy dispersive backscattering of electrons from surface resonances of a disordered medium and 1/f noise

Anderson localised states in the bulk of a disordered medium appear as sharp resonances near the surface. The resonant backscattering leads to an energy-dependent random time delay for an incident electron. We derive an analytic expression for the delay-time probability distribution at a given energy. This is shown to give a 1/f noise for the surface currents in general.

Local structure and magneto-transport in Sr2FeMoO6 oxides

Double perovskite oxides Sr2FeMoO6 have attracted a great interest for their peculiar magneto-transport properties, and, ill particular, for the large values of low-field magneto-resistance (MR) which remains elevated even at room temperature, thanks to their high Curie temperature (T-c > 400 K). These properties are strongly influenced by chemical cation disorder, that is by the relative arrangement of Fe and Mo on their sublattices: the regular alternation of Fe and Mo enhances the M R and saturation magnetization. On the contrary the disorder generally depresses the magnetization and worsen the MR response. In this work the X-ray absorption fine structure (XAFS) technique has been employed in order to probe the cation order from a local point of view. XAFS spectra were collected at the Fe and Mo K edges on Sr2FeMoO6 samples with different degree of long-range chemical order. The XAFS results prove that a high degree of short-range cation order is preserved, despite the different long-range order: the Fe-Mo correlations are always preferred over the Fe-Fe and Mo-Mo ones in the perfectly ordered as well as in highly disordered samples.

Influence of crossed electric and quantizing magnetic fields on the Einstein relation in nonlinear optical, optoelectronic and related materials: Simplified theory, relative comparison and suggestion for experimental determination

An attempt is made to study the Einstein relation for the diffusivity-to-mobility ratio (DMR) under crossed fields' configuration in nonlinear optical materials on the basis of a newly formulated electron dispersion law by incorporating the crystal field in the Hamiltonian and including the anisotropies of the effective electron mass and the spin-orbit splitting constants within the framework of kp formalisms. The corresponding results for III-V, ternary and quaternary compounds form a special case of our generalized analysis. The DMR has also been investigated for II-VI and stressed materials on the basis of various appropriate dispersion relations. We have considered n-CdGeAs2, n-Hg1-xCdxTe, n-In1-xGaxAsyP1-y lattice matched to InP, p-CdS and stressed n-InSb materials as examples. The DMR also increases with increasing electric field and the natures of oscillations are totally band structure dependent with different numerical values. It has been observed that the DMR exhibits oscillatory dependences with inverse quantizing magnetic field and carrier degeneracy due to the Subhnikov-de Haas effect. An experimental method of determining the DMR for degenerate materials in the present case has been suggested. (C) 2010 Elsevier B.V. All rights reserved.