Phase Equilibria in the System $Al_{2}O_{3}-CaO-CoO$ and Gibbs Energy of Formation of $Ca_{3}CoAl_{4}O_{10}$

The floating-zone method with different growth ambiences has been used to selectively obtain hexagonal or orthorhombic DyMnO3 single crystals. The crystals were characterized by x-ray powder diffraction of ground specimens and a structure refinement as well as electron diffraction. We report magnetic susceptibility, magnetization and specific heat studies of this multiferroic compound in both the hexagonal and the orthorhombic structure. The hexagonal DyMnO3 shows magnetic ordering of Mn3+ (S = 2) spins on a triangular Mn lattice at T-N(Mn) = 57 K characterized by a cusp in the specific heat. This transition is not apparent in the magnetic susceptibility due to the frustration on the Mn triangular lattice and the dominating paramagnetic susceptibility of the Dy3+ (S = 9/2) spins. At T-N(Dy) = 3 K, a partial antiferromagnetic order of Dy moments has been observed. In comparison, the magnetic data for orthorhombic DyMnO3 display three transitions. The data broadly agree with results from earlier neutron diffraction experiments, which allows for the following assignment: a transition from an incommensurate antiferromagnetic ordering of Mn3+ spins at T-N(Mn) = 39 K, a lock-in transition at Tlock-in = 16 K and a second antiferromagnetic transition at T-N(Dy) = 5 K due to the ordering of Dy moments. Both the hexagonal and the orthorhombic crystals show magnetic anisotropy and complex magnetic properties due to 4f-4f and 4f-3d couplings.

Axial binding of 2-methylimidazole to the tetraarylcarboxylatodiruthenium (II, III) core: X-ray crystal structure of [Ru-2(O2CC6H4-p-OMe)(4)(2-mimH)(2)](ClO4). 1.75CH(2)Cl(2).H2O

Diruthenium (II. III) complexes of the type [Ru-2(O2CAr)(4) (2-mimH)(2)](ClO4) (Ar = C6H4-p-X : X=OMe,1, X=Me, 2, 2-mimH=2-methylimidazole) have been isolated from the reaction of Ru2Cl(O2CAr)(4) with 2-mimH in CH2Cl2 followed by the addition of NaClO4. The crystal structure of 1.1.75CH(2)Cl(2).H2O has been determined. The crystal belongs to the monoclinic space group p2(1)/c with the following unit cell dimensions for the C40H40N4O16ClRu2.1.75CH(2)Cl(2).H2O (M = 1237.0) : a = 12.347(3)Angstrom, b = 17.615(5)Angstrom, c = 26.148(2)Angstrom,beta = 92.88(1)degrees. v = 5679(2)Angstrom(3). Z=4, D-c = 1.45 g cm(-3). lambda(Mo-K-alpha) = 0.7107 Angstrom, mu(Mo-K-alpha) = 8.1 cm(-1), T = 293 K, R = 0.0815 (wR(2) = 0.2118) for 5834 reflections with 1 > 2 sigma(I). The complex has a tetracarboxylatodiruthenium (II, III) core and two axially bound 2-methylimidazole ligands. The Ru-Ru bond length is 2.290(1)Angstrom. The Ru-Ru bond order is 2.5 and the complex is three-electron paramagnetic. The complex shows an irreversible Ru-2(II,III)-->Ru-2(Il,II) reduction near -0.2 V vs SCE in CH2Cl2-0. 1 MTBAP. The complexes exemplify the first adduct of the tetracarboxylatodiruthenium (II,III) core having N-donor ligands

Structure and magnetotransport properties of the layered manganites REl.2Srl.8Mn,07(R E = La, Pr, Nd)

We have examined the magnetotransport properties and the structure, by Rietveld refinement of powder X-ray data, of the phases RE(1.2)Sr(1.8)Mn(2)O(7) (RE = La, Pr, Nd). We find that on cooling, La1.2Sr1.8Mn2O7 undergoes a transition to a nearly perfect ferromagnet with 90% magnetization at 1.45 T, as reported by earlier workers, but the Pr and Nd phases show only a small magnetization that grows gradually as the temperature is decreased. There seems to be significant correlation between electrical transport and the Jahn-Teller elongation of the apical Mn-O bonds in these systems. The elongation of the apical Mn-O bonds forces the nine-coordinate rock-salt site to be occupied preferentially by the smaller rare-earth-metal cations. This preferential occupation is reliably obtained from the X-ray refinement. All three title phases show a magnetoresistance ratio of about 4(corresponding to a magnetoresistance, [R(0)-R(H)]/R(0), of about 75%) at a field of 7 T and temperatures around 100 K.

Electrical, structural and magnetic properties of polyaniline/pTSA-TiO2 nanocomposites

Polyaniline (PANI)/para-toluene sulfonic acid (pTSA) and PANI/pTSA-TiO2 composites were prepared using chemical method and characterized by infrared spectroscopy (IR), powder X-ray diffraction (XRD), scanning electron microscopy (SEM). The electrical conductivity and magnetic properties were also measured. In corroboration with XRD, the micrographs of SEM indicated the homogeneous dispersion of TiO nanoparticles in bulk PANI/pTSA matrix. Conductivity of the PANI/pTSA-TiO2 was higher than the PAN[/pTSA, and the maximum conductivity obtained was 9.48 (S/cm) at 5 wt% of TiO2. Using SQUID magnetometer, it was found that PANI/pTSA was either paramagnetic or weakly ferromagnetic from 300 K down to 5 K with H-C approximate to 30 Oe and M-r approximate to 0.015 emu/g. On the other hand,PANI/pTSA-TiO2 was diamagnetic from 300 K down to about 50 K and below which it was weakly ferromagnetic. Furthermore, a nearly temperature-independent magnetization was observed in both the cases down to 50 K and below which the magnetization increased rapidly (a Curie like susceptibility was observed). The Pauli susceptibility (chi(pauli)) was calculated to be about 4.8 X 10(-5) and 1.6 x 10(-5)emug(-1) Oe(-1) K for PANI/pTSA and PANI/pTSA-TiO2, respectively.

Photo-induced double-strand DNA and site-specific protein cleavage activity of L-histidine (mu-oxo)diiron(III) complexes of heterocyclic bases

Three oxo-bridged diiron(III) complexes of L-histidine and heterocyclic bases [Fe-2(mu-O)(L-his)(2)(B)(2)](ClO4)(2) (1-3), where B is 2,2'-bipyridine (bpy),1,10-phenanthroline (phen), dipyrido[3,2-d:2',3'-f]quinoxaline (dpq), were prepared and characterized. The bpy complex 1 was structurally characterized by X-ray crystallography. The molecular structure showed a {Fe-2(mu-O)} core in which iron(III) in a FeN4O2 coordination is bound to tridentate monoanionic L-histidine and bidentate bpy ligands. The Fe center dot center dot center dot Fe distance is similar to 3.5 angstrom. The Fe-O-Fe unit is essentially linear, giving a bond angle of similar to 172 degrees. The complexes showed irreversible cyclic voltammetric cathodic response near -0.1 V vs. SCE in H2O-0.1 M KCl. The binuclear units displayed antiferromagnetic interaction between two high-spin (S = 5/2) iron(III) centers giving a -J value of -110 cm(-1). The complexes showed good DNA binding propensity giving a binding constant value of similar to 10(5) M-1. Isothermal titration calorimetric data indicated single binding mode to the DNA. The binding was found to be driven by negative free energy change and enthalpy. The dpq complex 3 showed oxidative double-strand DNA cleavage on exposure to UV-A and visible light. The phen complex 2 displayed single-strand photocleavage of DNA. The DNA double-strand breaks were rationalized from theoretical molecular docking calculations. Mechanistic investigations showed formation of hydroxyl radicals as the reactive species through photodecarboxylation of the L-histidine ligand. The complexes exhibited good binding propensity to bovine serum albumin (BSA) protein in Tris-HCl/NaCl buffer medium. The dpq complex 3 showed UV-A light-induced site-specific oxidative BSA cleavage forming fragments of similar to 45 kDa and similar to 20 kDa molecular weights via SOH pathway.

Decarboxylation of arginine and ornithine by arginine decarboxylase purified from cucumber (Cucumis sativus) seedlings

A purified preparation of arginine decarboxylase from Cucumis sativus seedlings displayed ornithine decarboxylase activity as well. The two decarboxylase activities associated with the single protein responded differentially to agmatine, putrescine and Pi. While agmatine was inhibitory (50 %) to arginine decarboxylase activity, ornithine decarboxylase activity was stimulated by about 3-fold by the guanido arnine. Agmatine-stimulation of ornithine decarboxylase activity was only observed at higher concentrations of the amine. Inorganic phosphate enhanced arginine decarboxylase activity (2-fold) but ornithine decarboxylase activity was largely uninfluenced. Although both arginine and ornithine decarboxylase activities were inhibited by putrescine, ornithine decarboxylase activity was profoundly curtailed even at 1 mM concentration of the diamine. The enzyme-activated irreversible inhibitor for mammalian ornithine decarboxylase, viz. α-difluoromethyl ornithine, dramatically enhanced arginine decarboxylase activity (3-4 fold), whereas ornithine decarboxylase activity was partially (50%) inhibited by this inhibitor. At substrate level concentrations, the decarboxylation of arginine was not influenced by ornithine and vice-versa. Preliminary evidence for the existence of a specific inhibitor of ornithine decarboxylase activity in the crude extracts of the plant is presented. The above results suggest that these two amino acids could be decarboxylated at two different catalytic sites on a single protein.

Microemulsion-mediated synthesis of cobalt (pure fcc and hexagonal phases) and cobalt-nickel alloy nanoparticles

By choosing appropriate microemulsion systems, hexagonal cobalt (Co) and cobalt-nickel (1:1) alloy nanoparticles have been obtained with cetyltrimethylammonium bromide as a cationic surfactant at 500 degrees C. This method thus stabilizes the hcp cobalt even at sizes (<10 nm) at which normally fcc cobalt is predicted to be stable. On annealing the hcp cobalt nanoparticles in H-2 at 700 degrees C we could transform them to fcc cobalt nanoparticles. Microscopy studies show the formation of spherical nanoparticles of hexagonal and cubic forms of cobalt and Co-Ni (1:1) alloy nanoparticles with the average size of 4, 8 and 20 nm, respectively. Electrochemical studies show that the catalytic property towards oxygen evolution is dependent on the applied voltage. At low voltage (less than 0.65 V) the Co (hexagonal) nanoparticles are superior to the alloy (Co-Ni) nanoparticles while above this voltage the alloy nanoparticles are more efficient catalysts. The nanoparticles of cobalt (hcp and fcc) and alloy (Co-Ni) nanoparticles show ferromagnetism. The saturation magnetization of Co-Ni nanoparticles is reduced compared to the bulk possibly due to surface oxidation.

Phase separation versus spin glass behavior in La0.85Sr0.15CoO3

We present comprehensive studies of dc magnetization, ac susceptibility, and magnetotransport of two sets of La0.85Sr0.15CoO3 samples, one exhibits phase separation and the other exhibits spin glass behavior. Our study reveals that the phase separation in La0.85Sr0.15CoO3 is neither inherent nor ubiquitous; rather, it is a consequence of preparation condition. It is realized that the low temperature annealed sample exhibits phase separation while the high temperature annealed one shows the characteristic of spin glass behavior. This study shows that the most probable magnetic state of La0.85Sr0.15CoO3 is spin glass.

Quasi Crystalline A1-Mn Alloys: Pressure Induced Crystallization and Structural Studies

Irreversible, Pressure induced, quasicrystal-to-crystal transitions are observed for the first time in melt spun alloys at 4.9 GPa for Al 78 Mn22 and 9.3 GPa for Al86 Mn14 by monitoring the electrical resistivities of these alloys as a function of pressure. Electron diffraction and x-ray measurements are used to show that these quasicrystalline phases have icosohedral point group symmetry. The crystalline phases which appear at high pressures are identified as h.c.p. for Al78 Mn22 and orthorhombic for Al86 Mn14.

High pressure induced crystallization of rapidly solidified Al---Fe and Al---Mn quasi-crystalline alloysstar

The presence of phases showing icosahedral point symmetry was reported by Shechtman, Blech, Gratias and Cahn in rapidly quenched alloys of Al---Mn, Al---Fe and Al---Cr, and subsequently many other splat-cooled alloys with the i phase have been reported. In this paper we present the first results of high pressure experiments carried out on Al---Fe and Al---Mn quasi-crystals. The experiments performed at room temperature showed irreversible quasi-crystal-to-crystal transitions in Al---Mn and Al---Fe alloys. The transition pressures are 49 kbar for Al78Mn22, 93 kbar for Al86Mn14, 79 kbar for Al86Fe14, 54 kbar for Al82Fe18 and 108 kbar for Al75Fe25. The high pressure phases are found to be the equilibrium phases.

Magneto-structural study of a Cr-doped CaRuO3

Temperature-dependent neutron powder diffraction, magnetization and XPS studies were carried out on an optimally Cr-doped CaRuO3, i.e. CaRu0.85Cr0.15O3 (CRC-15). XPS data revealed that Cr exist in 3+ and 6+ oxidation states. The charge dissociation preserves the overall 4+ nominal charge of the Ru site. Although ferromagnetic correlations develop around 100 K, the system exhibits a large coercive field below 50 K. The unit cell volume exhibits negative thermal expansion below 50 K since the lattice expansion due to the magnetostrictive effect outweighs the thermal contraction due to the phonon-driven mechanism.

Kinetic mechanism of the interaction of D-cycloserine with serine hydroxymethyltransferase

The kinetic mechanism for the interaction of D-cycloserine with serine hydroxymethyltransferase (EC2.1.2.1) from sheep liver was established by measuring changes in the activity, absorbance, and circular dichoism (CD) of the enzyme. The irreversible inhibition of the enzyme was characterized by three detectable steps: an initial rapid step followed by two successive steps with rate constants of 5.4 X s-l and 1.4 X lo4 s-l. The first step was distinguished by a rapid disappearance of the enzyme absorbance peak at 425 nm, a decrease in the enzyme activity to 25% of the uninhibited velocity, and a lowering of the CD intensity at 432 nm to about 65% of the original value. The second step of the interaction was accompanied by a complete loss of enzyme.

Observation of reentrant spin glass behavior in LaCo0.5Ni0.5O3

The magnetic and transport properties of LaCo0.5Ni0.5O3 have been studied. The dc magnetization and the ac susceptibility studies suggest the presence of a magnetic-phase transition from a ferromagnetic (FM) to a spin glass phase at a low temperature. This type of reentrant spin-glass (RSG) behavior attached to a long-range ordered ferromagnet is observed in this system. A magnetoresistance of ~10% is observed at 5 K which is unsaturated up to 11 Tesla suggests the presence of antiferromagnetic (AFM) interactions. It is likely that the competition between such AFM interactions with FM interactions yield an RSG phase.

Visualization of enantiomers using natural abundant 13C-filtered single and double quantum selective refocusing experiments: Application to small chiral molecules

The routine use of proton NMR for the visualization of enantiomers, aligned in the chiral liquid crystal solvent poly-γ-benzyl-l-glutamate (PBLG), is restricted due to severe loss of resolution arising from large number of pair wise interaction of nuclear spins. In the present study, we have designed two experimental techniques for their visualization utilizing the natural abundance 13C edited selective refocusing of single quantum (CH-SERF) and double quantum (CH-DQSERF) coherences. The methods achieve chiral discrimination and aid in the simultaneous determination of homonuclear couplings between active and passive spins and heteronuclear couplings between the excited protons and the participating 13C spin. The CH-SERF also overcomes the problem of overlap of central transitions of the methyl selective refocusing (SERF) experiment resulting in better chiral discrimination. Theoretical description of the evolution of magnetization in both the sequences has been discussed using polarization operator formalism.

Effect of pressure on the electrical resistivity of bulk Ge20Te80 glass

An irreversible pressure induced semiconductor-to-metal transition in bulk Ge20Te80 glass is observed at about 5 GPa pressure. The high pressure phase has a face centered cubic structure with a lattice constant 6.42 A° as deduced by X-ray diffraction studies on the pressure quenched samples. The temperature and pressure dependence of the electrical resistivity confirms the observed transition to be a semiconductor-to-metal transition. The temperature dependence of thermo electric power is also reported.