Metastable extension of the fluorite phase field in Y2O3---ZrO2 and its effect on grain growth

Pure Y2O3 and Y2O3---ZrO2 solid solutions have been prepared by melt atomization and by pyrolysis of nitrate solutions. Extended solubility is readily achieved in both techniques for the entire composition range investigated: melts with 0–30% ZrO2 and precursors with 0–50% ZrO2. However, solidification of under cooled droplets yields almost exclusively single phase powders with the structure of cubic yttria (D53). In contrast, the pyrolysis route leads to a sequence of metastable microstructures beginning with a nanocrystalline disordered fluorite-based (C1) solid solution. Further heating leads to the evolution of much larger (micron size) flake crystals with a {001} texture, concurrent with partial ordering of the oxygen ions to the sites occupied in the D53 structure. The driving force for ordering and the rate of grain growth decrease with increasing ZrO2 addition. Abrupt heating to high temperatures or electron irradiation can induce ordering without substantial grain growth. There is no significant reduction in porosity during the recrystallization, which with the other observations suggests that grain growth is driven by the free energy available for the ordering transformation from fluorite to the yttria structure. This route offers opportunities for single crystal thin film development at relatively low processing temperatures.

Metastable extension of the fluorite phase field in Y2O3---ZrO2 and its effect on grain growth

Pure Y2O3 and Y2O3-ZrO2 solid solutions have been prepared by melt atomization and by pyrolysis of nitrate solutions. Extended solubility is readily achieved in both techniques for the entire composition range investigated: melts with 0-30% ZrO2 and precursors with 0-50% ZrO2. However, solidification of under cooled droplets yields almost exclusively single phase powders with the structure of cubic yttria (D5(3)). In contrast, the pyrolysis route leads to a sequence of metastable microstructures beginning with a nanocrystalline disordered fluorite-based (C1) solid solution. Further heating leads to the evolution of much larger (micron size) flake crystals with a {001} texture, concurrent with partial ordering of the oxygen ions to the sites occupied in the D5(3) structure. The driving force for ordering and the rate of grain growth decrease with increasing ZrO2 addition. Abrupt heating to high temperatures or electron irradiation can induce ordering without substantial grain growth. There is no significant reduction in porosity during the recrystallization, which with the other observations suggests that grain growth is driven by the free energy available for the ordering transformation from fluorite to the yttria structure. This route offers opportunities for single crystal thin film development at relatively low processing temperatures.

Physical characterization of the organic nonlinear optical crystal � 3-methoxy 4-hydroxy benzaldehyde

We highlight our recent experimental work on an efficient molecular nonlinear optical crystal, 3-methoxy 4-hydroxy benzaldehyde (MHBA). Optical quality single crystals of MHBA were grown from mixtures of solvents and from melt. The overall absorption and transparency window were improved by growing them in a mixture of chloroform and acetone. The grown crystals were characterized for their optical transmission, mechanical hardness and laser damage. We have observed a strong correlation between mechanical properties and laser induced damage.

Fatigue crack propagation model and size effect in concrete using dimensional analysis

It is well known that fatigue in concrete causes excessive deformations and cracking leading to structural failures. Due to quasi-brittle nature of concrete and formation of a fracture process zone, the rate of fatigue crack growth depends on a number of parameters, such as, the tensile strength, fracture toughness, loading ratio and most importantly the structural size. In this work, an analytical model is proposed for estimating the fatigue crack growth in concrete by using the concepts of dimensional analysis and including the above parameters. Knowing the governed and the governing parameters of the physical problem and by using the concepts of self-similarity, a relationship is obtained between different parameters involved. It is shown that the proposed fatigue law is able to capture the size effect in plain concrete and agrees well with different experimental results. Through a sensitivity analysis, it is shown that the structural size plays a dominant role followed by loading ratio and the initial crack length in fatigue crack propagation. (C) 2010 Elsevier Ltd. All rights reserved.

Crystal structure of Salmonella typhimurium 2-methylcitrate synthase: Insights on domain movement and substrate specificity

2-Methylcitric acid (2-MCA) cycle is one of the well studied pathways for the utilization of propionate as a source of carbon and energy in bacteria such as Salmonella typhimurium and Escherichia coli. 2-Methylcitrate synthase (2-MCS) catalyzes the conversion of oxaloacetate and propionyl-CoA to 2-methylcitrate and CoA in the second step of 2-MCA cycle. Here, we report the X-ray crystal structure of S. typhimurium 2-MCS (StPrpC) at 2.4 A resolution and its functional characterization. StPrpC was found to utilize propionyl-CoA more efficiently than acetyl-CoA or butyryl-CoA. The polypeptide fold and the catalytic residues of StPrpC are conserved in citrate synthases (CSs) suggesting similarities in their functional mechanisms. In the triclinic P1 cell, StPrpC molecules were organized as decamers composed of five identical dimer units. In solution, StPrpC was in a dimeric form at low concentrations and was converted to larger oligomers at higher concentrations. CSs are usually dimeric proteins. In Gram-negative bacteria, a hexameric form, believed to be important for regulation of activity by NADH, is also observed. Structural comparisons with hexameric E. coil CS suggested that the key residues involved in NADH binding are not conserved in StPrpC. Structural comparison with the ligand free and bound states of CSs showed that StPrpC is in a nearly closed conformation despite the absence of bound ligands. It was found that the Tyr197 and Leu324 of StPrpC are structurally equivalent to the ligand binding residues His and Val, respectively, of CSs. These substitutions might determine the specificities for acyl-CoAs of these enzymes. (C) 2010 Elsevier Inc. All rights reserved.

Role of organic fluorine in crystal engineering

The design of compounds with novel and improved physico-chemical properties as advanced functional materials with a specific application spectrum requires the knowledge about possible supramolecular packing motifs and their experimental control in crystalline lattice. Besides the structure of the individual molecule, non-covalent interactions play a significant role in the determination of molecular conformation, along with the formation of three-dimensional supramolecular architecture in a crystal as a requirement for molecular recognition processes, and the related bioactivity. Involvement of functional groups will contribute to the formation of a predefined packing motif due to their well-defined interactions. The strength and directionality of these interactions create characteristic packing motifs, which can be used for the design of supramolecular arrangements by the development of appropriate strategies for the precise control of their topology. Most relevant of these non-covalent interactions are stacking interactions and hydrogen bonds, which have been subjects of extensive study in the last two decades. In recent literature, substantial efforts have been put in by various researchers towards the understanding of interactions involving organic fluorine and the role they play in generating different packing motifs which guides assembling of molecules in the crystal lattice.

Studies in crystal engineering: structure�reactivity correlations of substituted styrylcoumarins and related systems

The solid state photochemical behaviour of 7-hydroxy-4-styrylcoumarin 1 and several of its derivatives and analogues has been investigated. All the compounds with the exception of 7-methoxy-4-styrylcoumarin 2 are photolabile and yield anti-HT dimers. It has been observed that chloro substitution in the systems studied does not lead to the expected beta-packing mode. The photobehaviour of 1 and 2 has been correlated with their crystal structures. Reasons for alpha-packing have been examined. The systematics in the arrangement of the carbonyl group and phenyl group of the close neighbours in the crystals of 1, 2 and a few other cases are presented.

Reactions of palladium chloride with amino spirocyclic cyclotriphosphazenes: Isolation and Crystal Structures of Novel Mono- and Bimetallic Complexes Formed by the Hydrolysis of a .lambda.5-Diazaphospholane Ring

The reaction of the amino spirocyclic cyclotriphosphazene N3P3(NMe2)4(NHCH2CH2CH2NH) (2) with palladium chloride gives the stable chelate complex [PdCl2.2] (4). An X-ray crystallographic study reveals that one of the nitrogen atoms of the diaminoalkane moiety and an adjacent phosphazene ring nitrogen atom are bonded to the metal. An analogous reaction with the phosphazene N3P3(NMe2)4(NHCH2CH2NH) (1) gives initially a similar complex which undergoes facile hydrolysis to give the novel monometallic and bimetallic complexes [PdCl2.HN3P3(O)(NMe2)4(NHCH2CH2NH2)] (5) and [PdCl{N3P3(NMe2)4(NCH2CH2NH2)}]2(O) (6), which have been structurally characterized; in the former, an (oxophosphazadienyl)ethylenediamine is chelated to the metal whereas, in the latter, an oxobridged bis(cyclotriphosphazene) acts as a hexadentate nitrogen donor ligand in its dianionic form. Crystal data for 4 : a = 14.137(1) angstrom, b = 8.3332(5) angstrom, c = 19.205(2) angstrom, beta = 96.108(7)degrees, P2(1)/c, Z = 4, R = 0.027 with 3090 reflections (F > 5sigma(F)). Crystal data for 5 : a = 8.368(2) angstrom, b = 16.841(4) A, c = 16.092(5) angstrom, beta = 98.31(2)degrees, P2(1)/n, Z = 4, R = 0.049 with 3519 reflections (F > 5sigma(F)). Crystal data for 6 : a = 22.455(6) angstrom, b = 14.882(3) angstrom, c = 13.026(5) angstrom, 6 = 98.55(2)degrees, C2/c, Z = 4, R = 0.038 with 3023 reflections (F > 5sigma(F)).

Synthesis and x-ray crystal structure of a CuII-theophylline complex: [Cu(theo)2 (H2O)3]·2H2O

The complex [Cu-II (theo)(2)(H2O)(3)].2H(2)O (theo = theophylline) was obtained from aqueous solution. The crystals belong to the monoclinic system, space group P2(1)/n, and are reflection twins about the (001) face. The structure was solved using data from a twinned crystal and refined to final R and R(W) values of 0.069 and 0.064, respectively. Copper has a square-pyramidal coordination with two thee molecules coordinating through N(7) at equatorial positions. The remaining sites are occupied by water molecules. O(6) of one of the thee molecules is at the other axial site at a longer distance of 3.18 Angstrom. This could lead to an alternate (4+1+1) octahedral coordination geometry for Cu-II. The packing is stabilized by stacking interactions between the theophylline moieties at an average separation of 3.46 Angstrom.

Synthesis, Crystal Structure, and Magnetic Properties of a Ferromagnetically Coupled Angular Trinuclear Copper(11) Complex [Cu3(02CMe)4(bpy)s(HzO)](PF)62

The synthesis, X-ray crystal structure, and magnetic properties of an angular trinuclear copper(II) complex [Cu3(O2CMC)4(bpy)3(H2O)](PF6)2 (1), obtained from a reaction of Cu2(O2CMe)4(H2O)2 With 2,2'-bipyridine (bpy) and NH4PF6 in ethanol, are reported. Complex 1 crystallizes in triclinic space group P1BAR with a = 11.529(1) angstrom, b = 12.121(2) angstrom, c = 17.153(2) angstrom, alpha = 82.01(1)-degrees, beta = 79.42(1)-degrees, gamma = 89.62(1)-degrees, and Z = 2. A total of 6928 data with I > 2.5sigma(I) were refined to R = 0.0441 and R(w) = 0.0557. The structure consists of a trinuclear core bridged by four acetate ligands showing different bonding modes. The coordination geometry at each copper is distorted square-pyramidal with a CuN2O2...O chromophore. The Cu...Cu distances are 3.198(1) angstrom, 4.568(1) angstrom, and 6.277(1) angstrom. There are two monoatomic acetate bridges showing Cu-O-Cu angles of 93.1(1) and 97.5(1)-degrees. Magnetic studies in the temperature range 39-297 K show the presence of a strong ferromagnetically coupled dicopper(II) unit (2J = +158 cm-1) and an essentially isolated copper(II) center (2J' = -0.4 cm-1) in 1. The EPR spectra display an axial spectrum giving g(parallel-to) = 2.28 (A(parallel-to) = 160 X 10(-4) cm-1) and g(perpendicular-to) = 2.06 (A(perpendicular-to) = 12 X 10(-4) cm-1) for the normal copper and two intense isotropic signals with g values 2.70 and 1.74 for the strongly coupled copper pair. The structural features of 1 compare well with the first generation models for ascorbate oxidase.

Reflections on the Hydrogen Bond in Crystal Engineering

Comments on aspects of the new definition of the hydrogen bond specific to crystal engineering are given.