Enhanced Ion Anisotropy by Nonconventional Coordination Geometry: Single-Chain Magnet Behavior for a [{(FeL)-L-II}(2){Nb-IV(CN)(8)}] Helical Chain Compound Designed with Heptacoordinate Fe-II

Nonconventional heptacoordination in combination with efficient magnetic exchange coupling is shown to yield a 1-D heteronuclear {(FeNbIV)-Nb-II} compound with remarkable magnetic features when compared to other Fe(II)-based single chain magnets (SCM). Cyano-bridged heterometallic {3d-4d} and {3d-5d} chains are formed upon assembling Fe(II) bearing a pentadentate macrocycle as the blocking ligand with octacyano metallates, [M(CN)(8)](4-) (M = Nb-IV, Mo-IV, W-IV.) X-ray diffraction (single-crystal and powder) measurements reveal that the [{(H2O)Fe(L-1)}{M(CN)(8)}{Fe(L-1)}](infinity) architectures consist of isomorphous 1-D polymeric structures based on the alternation of {Fe(L-1)}(2+) and {M(CN)(8)}(4-) units (L-1 stands for the pentadentate macrocycle). Analysis of the magnetic susceptibility behavior revealed cyano-bridged {Fe-Nb} exchange interaction to be antiferromagnetic with J = -20 cm(-1) deduced from fitting an Ising model taking into account the noncollinear spin arrangement. For this ferrimagnetic chain a slow relaxation of its magnetization is observed at low temperature revealing a SCM behavior with Delta/k(B) = 74 K and tau(0) = 4.6 x 10(-11) s. The M versus H behavior exhibits a hysteresis loop with a coercive field of 4 kOe at 1 K and reveals at 380 mK magnetic avalanche processes, i.e., abrupt reversals in magnetization as H is varied. The origin of these characteristics is attributed to the combination of efficient {Fe-Nb} exchange interaction and significant anisotropy of the {Fe(L-1)) unit. High field EPR and magnetization experiments have revealed for the parent compound [Fe(L-1)(H2O)(2)]Cl-2 a negative zero field splitting parameter of D approximate to -17 cm(-1). The crystal structure, magnetic behavior, and Mossbauer data for [Fe(L-1)(H2O)(2)]Cl-2 are also reported.

Solution-Combustion Synthesized Nanocrystalline Li4Ti5O12 As High-Rate Performance Li-Ion Battery Anode

Nanocrystalline Li4Ti5O12 (LTO) crystallizing in cubic spinel-phase has been synthesized by single-step-solution-combustion method in less than one minute. LTO particles thus synthesized are flaky and highly porous in nature with a surface area of 12 m(2)/g. Transmission electron micrographs indicate the primary particles to be agglomerated crystallites of varying size between 20 and 50 nm with a 3-dimensional interconnected porous network. During their galvanostatic charge-discharge at varying rates, LTO electrodes yield a capacity value close to the theoretical value of 175 mA h/g at C/2 rate. The electrodes also exhibit promising capacity retention with little capacity loss over 100 cycles at varying discharge rates together with attractive discharge-rate capabilities yielding capacity values of 140 mA h/g and 70 mA h/g at 10 and 100 C discharge rates, respectively. The ameliorated electrode-performance is ascribed to nano and highly porous morphology of the electrodes that provide short diffusion-paths for Li in conjunction with electrolyte percolation through the electrode pores ensuring a high flux of Li.

Consideration on thermal decomposition of calcium hydroxide pellets for energy storage

The reversible chemical reaction of Ca(OH)2/CaO appears to be attractive for storage of solar thermal energy, in view of the nonpolluting and nontoxic nature of the reactants. This paper presents some data on thermal decomposition of calcium hydroxide pellets along with its additives of aluminum, aluminum hydroxide, zinc, and copper. The addition of aluminum and zinc powder enhanced the rate of decomposition considerably at 450°C, but copper had no effect. Considerations on the effect of additives are also discussed in some detail, though their effects are not established with certainty. There is some evidence that heat transfer into the pellet, and the number of potential nucleation sites due to thermal stresses, influence the kinetics and mechanism of decomposition.

New family of thallium cuprate superconductors not containing calcium or barium: TlSrn+1−xLnxCunO2n+3+δ (Ln=La, Pr, or Nd)

The first two members of the new TlSrn+1−xLnxCunO2n+3+δ (Ln=La, Pr, or Nd) series of superconducting cuprates possessing 1021 and 1122 type structures are described. The n=1 (1021) members with Tcs around 40 K have electrons or holes as the majority charge carriers depending on x. The n=2 (1122) cuprate (Ln=Pr or Nd) shows a Tc in the 80–90 K range.

A chemical approach to an understanding of the fast ion conduction in silver iodide-silver oxysalt glasses

A number of AgI based fast ion conducting glasses, with a general formula AgI---Ag2O---MxOy (MxOy=MoO3, SeO3, WO3, V2O5, P2O5, GeO2, B2O3, As2O3, CrO3) have been studied. A chemical approach is made to investigate the origin of fast ion conduction in these glasses. An index known as Image tructural Image npinning Image umber, SUN (S), has been defined for the purpose, based on the unscreened nuclear charge of silver ions and the equilibrium lectronegativities of the halide-oxyanion matrix in these glasses. The variation of the glass transition temperature, Tg, conductivity, σ, and the energy of activation, Ea, with the concentration of AgI are discussed in the light of the structural unpinning number. Conductivities increase uniformly in any given glass series as a smooth function of S and level off at very high values. The entire range of conductivity appears to vary as ln Image , where ln σ0 corresponds roughly to the conductivity of the hypothetical AgI glass and “a” is a constant which could be obtained as the slope in the graph of ln Ea versus S. It is suggested that the increase in the concentration of AgI beyond 75–80 mole% in the glass is not advantageous from the conductivity point of view.

Effect of calcium deficiency on the mechanical properties of hydroxyapatite crystals

The deterioration of the mechanical properties of bone with age is related to several factors including the structure, organization and chemistry of the constituent phases; however, the relative contribution of each of these factors is not well understood. In this study, we have investigated the effect of chemistry (calcium deficiency) on the mechanical properties of single crystals of hydroxyapatite. Single crystals of stoichiometric crystals grown by the flux method and calcium-deficient platelet crystals grown using wet chemical methods were used as model systems. Using nanoindentation, we show that calcium deficiency leads to an 80% reduction in the hardness and elastic modulus and at least a 75% reduction in toughness in plate-shaped hydroxyapatite crystals. Measurement of local mechanical properties using nanoindentation and nanoscale chemistry through elemental mapping in a transmission electron microscope points to a direct correlation between the observed spatial variation in composition and the large scatter in the measured hardness and modulus values. (C) 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Redistribution of subcellular calcium in rat liver on administration of vanadate

Mitochondria isolated from the livers of rats administered with sodium meta-, ortho-, or polyvanadate, but not vanadyl sulphate, exhibited enhanced Ca2+ — stimulated respiration and uptake of calcium. These effects were shown also by mitochondria isolated from livers perfused with polyvanadate. The concentration of acid-soluble calcium decreased significantly in the mitochondrial fraction on vanadate treatment, while that in the cytosol showed a corresponding increase. Phenoxybenzamine, an antagonist to a-adrenergic receptors, effectively inhibited vanadate-induced Ca2+ mobilization, but surgical sympathectomy was without effect. This is the first demonstration of vanadate mimicking agr-adrenergic agonists in vivo.

Molecular theory of solvation and solvation dynamics of a classical ion in a dipolar liquid

A microscopic theory of equilibrium solvation and solvation dynamics of a classical, polar, solute molecule in dipolar solvent is presented. Density functional theory is used to explicitly calculate the polarization structure around a solvated ion. The calculated solvent polarization structure is different from the continuum model prediction in several respects. The value of the polarization at the surface of the ion is less than the continuum value. The solvent polarization also exhibits small oscillations in space near the ion. We show that, under certain approximations, our linear equilibrium theory reduces to the nonlocal electrostatic theory, with the dielectric function (c(k)) of the liquid now wave vector (k) dependent. It is further shown that the nonlocal electrostatic estimate of solvation energy, with a microscopic c(k), is close to the estimate of linearized equilibrium theories of polar liquids. The study of solvation dynamics is based on a generalized Smoluchowski equation with a mean-field force term to take into account the effects of intermolecular interactions. This study incorporates the local distortion of the solvent structure near the ion and also the effects of the translational modes of the solvent molecules.The latter contribution, if significant, can considerably accelerate the relaxation of solvent polarization and can even give rise to a long time decay that agrees with the continuum model prediction. The significance of these results is discussed.

Novel organic porous solids with channel and layered structures from 1,3,5-triazine-2,4,6-triaminehexaacetic acid and its calcium salt

Single crystals of a symmetrically substituted molecule, 1,3,5-triazine-2,4,6-triaminehexaacetic acid, (TTHA) and its Ca2+ salt have been synthesized, the analysis of which reveals the existence of novel channel type cavities and helical packing organizations in the crystals.

High-Resolution Magic Angle Spinning Nmr-Studies Of P-31 And B-11 In Fast Ion Conducting Agi-Ag2o-P2o5 And Agi-Ag2o-B2o3 Glasses

Silver iodide-based fast ion conducting glasses containing silver phosphate and silver borate have been studied. An attempt is made to identify the interaction between anions by studying the chemical shifts of31P and11B atoms in high resolution (HR) magic angle spinning (MAS) NMR spectra. Variation in the chemical shifts of31P or11B has been observed which is attributed to the change in the partial charge on the31P or11B. This is indicative of the change in the electronegativity of the anion matrix as a whole. This in turn is interpreted as due to significant interaction among anions. The significance of such interaction to the concept of structural unpinning of silver ions in fast ion conducting glasses is discussed.

Metal-ion-ligand interactions in thermotropic liquid crystals

The interactions of lithium perchlorate with ligands such as dimethyl sulphoxide, acetonitrile, pyridine and the Schiff base liquid crystals are investigated. The experiments open a new field for the study of metal-ion-ligand interactions in thermotropic liquid crystals.

Quinone studies. Part III. Metal ion-catalysed oxidation of halophenols and halonaphthols by peroxidisulphate

Oxidation of representative halophenols and halonaphthols by peroxidisulphate has been examined. The influence of metallic ions, viz. Cu2+, Fe3+, Ag+, on the above reaction has been studied. Cu2+ ion-catalyzed oxidation gives halo-1, 4-quinones in excellent yield. Potassium bis(biureto)cuprate(III) complex also oxidises halophenols to halo-1, 4-quinones.

ESR studies of X-irradiated strontium mixed calcium tartrate crystals

The electron spin resonance spectra of X-ray irradiated single crystals of strontium doped calcium tartrate tetrahydrate (CST) with molecular formula Ca0.88Sr0.12C4H4O6.4H(2)O grown in gels has been investigated. Only one species of free radical but with two magnetically unequivalent sites was observed at room temperature. The free radical was found to be the result of the splitting of a C-II bond adjacent to both the hydroxyl and carboxyl groups. The a factor was found to be slightly anisotropic. Couplings with two H nuclei, believed to be the proton of the OH group attached directly to the unsaturated asymmetric carbon atom and the proton attached directly to the: other asymmetric carbon atom of the molecule were observed. The principal g-values were found to be 2.0030, 2.0017, 2.0027. The principal elements of the nuclear coupling are 7.45, 6.59, 4.28 and 8.56, 7.22, 18.71 G, respectively. The radical was found to be very stable. (C) 2000 Elsevier Science Ltd. All rights reserved.

Solvation of an ion and of a dipole in a dipolar liquid: How different are the dynamics

Theoretical expressions for the time-dependent solvation energy of an ion and of a dipole in a dense dipolar liquid are derived from microscopic considerations. We show that in contradiction to the prediction of the continuum models, the dynamics of these two species are significantly different from each other. Especially, the zero wavevector contribution, which is significant for ions, is totally absent for dipoles. Dipolar solvation may be profoundly influenced by the translational modes of the host solvent.