Nonstoichiometry, defects and thermodynamic properties of YFeO3, YFe2O4 and Y3Fe5O12

Oxygen nonstoichiometry of three ternary oxides. YFeO3-delta, YFe2O4-alpha and Y3Fe5O12-theta. in the system Y-Fe-O was investigated as a function of oxygen partial pressure by thermogravimetry at high temperature. The defects responsible for nonstoichiometry were identified as oxygen vacancies for YFeO3-delta and YFe2O4-alpha although the manner of variation of nonstoichiometric parameter with oxygen partial pressure for these two oxides is quite different. Cation interstitials are the predominant defects in Y3Fe5O12-theta. Gibbs energies of formation of the three nonstoichiometric oxides were determined using solid-state electrochemical cells in the temperature range from 975 to 1475 K. YFe2O4-alpha was found to be stable only above 1391 K. Gibbs energies of formation of the three stoichiometric compounds from their component binary oxides were obtained by combining information from solid state cells with results of thermogravimetric analysis using the Gibbs-Duhem relation. The results can be summarized as: (1/2)Y2O3 + (1/2)Fe2O3 -> YFeO3;Delta G(f(ox))(O)(+/- 250)(J/mol) = 17, 126-8.263T (1/2)Y2O3 + FeO + (1/2)Fe2O3 -> YFe2O4;Delta G(f(ox))(O)(+/- 260)(J/mol) = -10,352-13.24T (3/2)Y2O3 + (5/2)Fe2O3 -> Y3Fe5O12;Delta G(f(ox))(O)(+/- 780)(J/mol) = -56, 647-31.091T. (C) 2012 Elsevier B.V. All rights reserved.

A new method for fracture toughness determination of graded (Pt,Ni)Al bond coats by microbeam bend tests

A novel method is proposed for fracture toughness determination of graded microstructurally complex (Pt,Ni)Al bond coats using edge-notched doubly clamped beams subjected to bending. Micron-scale beams are machined using the focused ion beam and loaded in bending under a nanoindenter. Failure loads gathered from the pop-ins in the load-displacement curves combined with XFEM analysis are used to calculate K-c at individual zones, free from substrate effects. The testing technique and sources of errors in measurement are described and possible micromechanisms of fracture in such heterogeneous coatings discussed.

Anticancer Activity of Hydrogen-Bond-Stabilized Half-Sandwich RuII Complexes with Heterocycles

Neutral half-sandwich organometallic ruthenium(II) complexes of the type (?6-cymene)RuCl2(L)] (H1H10), where L represents a heterocyclic ligand, have been synthesized and characterized spectroscopically. The structures of five complexes were also established by single-crystal X-ray diffraction confirming a piano-stool geometry with ?6 coordination of the arene ligand. Hydrogen bonding between the N?H group of the heterocycle and a chlorine atom attached to Ru stabilizes the metalligand interaction. Complexes coordinated to a mercaptobenzothiazole framework (H1) or mercaptobenzoxazole (H6) showed high cytotoxicity against several cancer cells but not against normal cells. In vitro studies have shown that the inhibition of cancer cell growth involves primarily G1-phase arrest as well as the generation of reactive oxygen species (ROS). The complexes are found to bind DNA in a non-intercalative fashion and cause unwinding of plasmid DNA in a cell-free medium. Surprisingly, the cytotoxic complexes H1 and H6 differ in their interaction with DNA, as observed by biophysical studies, they either cause a biphasic melting of the DNA or the inhibition of topoisomerase IIa activity, respectively. Substitution of the aromatic ring of the heterocycle or adding a second hydrogen-bond donor on the heterocycle reduces the cytotoxicity.

Reactions of Titanocene Bis(trimethylsilyl)acetylene Complexes with Carbodiimides: An Experimental and Theoretical Study of Complexation versus C-N Bond Activation

The reaction of the low valent metallocene(II) sources Cp'Ti-2(eta(2)-Me3SiC2SiMe3) (Cp' = eta(5)-cyclopentadienyl, 1a or eta(5)-pentamethylcyclopentadienyl, 1b) with different carbodiimide substrates RN=C=NR' 2-R-R' (R = t-Bu; R' = Et; R = R' = i-Pr; t-Bu; SiMe3; 2,4,6-Me-C6H2 and 2,6-i-Pr-C6H3) was investigated to explore the frontiers of ring strained, unusual four-membered heterometallacycles 5-R. The product complexes show dismantlement, isomerization, or C-C coupling of the applied carbodiimide substrates, respectively, to form unusual mono-, di-, and tetranuclear titanium(III) complexes. A detailed theoretical study revealed that the formation of the unusual complexes can be attributed to the biradicaloid nature of the unusual four-membered heterometallacycles 5-R, which presents an intriguing situation of M-C bonding. The combined experimental and theoretical study highlights the delicate interplay of electronic and steric effects in the stabilization of strained four-membered heterometallacycles, accounting for the isolation of the obtained complexes.

ZnO/Poly(3,4-ethylenedioxythiophene) Poly(styrenesulfonate) Based Ultraviolet and Visible Photodetectors: Role of Defects

Here, we report the ZnO/poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) based photodetectors that can response to ultraviolet as well as visible light. The temporal response of the heterostructures for various excitations in the ultraviolet (UV) and visible range are performed. The time constants are found to be excitation-dependent, the response to visible light is better as compared to UV. The reason behind the better response to UV light is the high level of defects present in ZnO as confirmed by the photoluminescence (PL) measurements. This is corroborated by the time resolved fluorescence (TRF) measurements which provides sufficient information behind the slow response time under the UV excitations. The possible explanation being the non-radiative recombinations occurring due to the traps or impurities present in the film which slows down the photoresponse.

B-H Bond Activation Using an Electrophilic Metal Complex: Insights into the Reaction Pathway

A highly electrophilic ruthenium center in the RuCl(dppe)(2)]OTf] complex brings about the activation of the B H bond in ammonia borane (H3N center dot BH3, AB) and dimethylamine borane (Me2HN center dot BH3, DMAB). At room temperature, the reaction between RuCl(dppe)(2)]OTf] and AB or DMAB results in trans-RuH(eta(2)-H-2)(dppe)(2)]OTf] trans-RuCl(eta(2)-H-2)(dppe)(2)]OTf], and trans-RuH(Cl)(dppe)(2)], as noted in the NMR spectra. Mixing the ruthenium complex and AB or DMAB at low temperature (198/193 K) followed by NMR spectral measurements as the reaction mixture was warmed up to room temperature allowed the observation of various species formed enroute to the final products that were obtained at room temperature. On the basis of the variable-temperature multinuclear NMR spectroscopic studies of these two reactions, the mechanistic insights for B-H bond activation were obtained. In both cases, the reaction proceeds via an eta(1)-B-H moiety bound to the metal center. The detailed mechanistic pathways of these two reactions as studied by NMR spectroscopy are described.

Charge Density Analysis of Ferulic Acid: Robustness of a Trifurcated C-H center dot center dot center dot O Hydrogen Bond

The toplogical features of a sporadic trifurcated C-H center dot center dot center dot O interaction region, where an oxygen atom acts as an acceptor of three weak hydrogen bonds, has been investigated by experimental and theoretical charge density analysis of ferulic acid. The interaction energy of the asymmetric molecular dimer formed by the trifurcated C-H center dot center dot center dot O motif, based on the multipolar model, is shown to be greater than the corresponding asymmetric O-H center dot center dot center dot O dimer in this crystal structure. Further, the hydrogen bond energies associated with these interaction motifs have been estimated from the local kinetic and potential energy densities at the bond critical points. The trends suggest that the interaction energy of the trifurcated C-H center dot center dot center dot O region is comparable to that of a single O-H center dot center dot center dot O hydrogen bond.

Electrophile-Induced C-C Bond Activation of Vinylcyclopropanes for the Synthesis of Z-Alkylidenetetrahydrofurans

We present a detailed study on the behavior of vinylcyclopropanes as masked donor acceptor system toward the stereoselective synthesis of Z-alkylidenetetrahydrofurans. Results of bromenium catalyzed indirect activation of C-C bond of vinylcyclopropanes and concomitant cyclization to alkylidenetetrahydrofuran and other heterocycles have been discussed. The stereoselective formation of the Z-isomer is strongly controlled by the extent of destabilization of one of the gauche conformers of the vinylcyclopropane. The ring-opening/cyclization step was found to be stereospecific as in the case of DA cyclopropanes. The activation of the C-C bond leads to a tight-carbocation intermediate, which is evident from the complete retention of the stereochemistry. The retention of configuration has been established by a necessary control experiment that rules out the possibility of a double inversion pathway. The present results serve as direct stereochemical evidence in support of a tight ion-pair intermediate versus the controversial S(N)2 pathway. A 2D potential energy scan has been carried out at B3LYP/6-31G(d) level theory to obtain the relative energies of the conformers. The Z-selectivity observed has been explained on the basis of the relative population of the conformers and modeling the intermediate and transition state involved in the reaction at M06-2x/6-31+G(d) level. Energy profile for the cyclization step was modeled considering various possible pathways through which cyclization can happen. The methodology has been successfully demonstrated on vinylcyclobutanes as well.

Engagement of CF3 Group in N-H center dot center dot center dot F-C Hydrogen Bond in the Solution State: NMR Spectroscopy and MD Simulation Studies

Unambiguous evidence for the engagement of CF3 group in N-H center dot center dot center dot F-C hydrogen bond in a low polarity solvent, the first observation of its kind, is reported. The presence of such weak molecular interactions in the solution state is convincingly established by one and two-dimensional H-1, F-19, and natural abundant N-15 NMR spectroscopic studies. The strong and direct evidence is derived by the observation of through-space couplings, such as, (1h)J(FH), (1h)J(FN), and (2h)J(FF), where the spin polarization is transmitted through hydrogen bond. In an interesting example of a molecule containing two CF3 groups getting simultaneously involved in hydrogen bond, where hydrogen bond mediated couplings are not reflected in the NMR spectrum, F-19-F-19 NOESY experiment yielded confirmatory evidence. Significant deviations in the strengths of (1)J(NH), variable temperature, and the solvent induced perturbations yielded additional support. The NMR results are corroborated by both DFT calculations and MD simulations, where the quantitative information on different ways of involvement of fluorine in two and three centered hydrogen bonds, their percentage of occurrences, and geometries have been obtained. The hydrogen bond interaction energies have also been calculated.

Dramatic Structural Changes Resulting from the Loss of a Crucial Hydrogen Bond in the Hinge Region Involved in C-Terminal Helix Swapping in SurE: A Survival Protein from Salmonella typhimurium

Domain swapping is an interesting feature of some oligomeric proteins in which each protomer of the oligomer provides an identical surface for exclusive interaction with a segment or domain belonging to another protomer. Here we report results of mutagenesis experiments on the structure of C-terminal helix swapped dimer of a stationary phase survival protein from Salmonella typhimurium (StSurE). Wild type StSurE is a dimer in which a large helical segment at the C-terminus and a tetramerization loop comprising two beta strands are swapped between the protomers. Key residues in StSurE that might promote C-terminal helix swapping were identified by sequence and structural comparisons. Three mutants in which the helix swapping is likely to be avoided were constructed and expressed in E. coli. Three-dimensional X-ray crystal structures of the mutants H234A and D230A/H234A could be determined at 2.1 angstrom and 2.35 angstrom resolutions, respectively. Contrary to expectations, helix swapping was mostly retained in both the mutants. The loss of the crucial D230 OD2- H234 NE2 hydrogen bond (2.89 angstrom in the wild type structure) in the hinge region was compensated by new inter and intra-chain interactions. However, the two fold molecular symmetry was lost and there were large conformational changes throughout the polypeptide. In spite of these changes, the dimeric structure and an approximate tetrameric organization were retained, probably due to the interactions involving the tetramerization loop. Mutants were mostly functionally inactive, highlighting the importance of precise inter-subunit interactions for the symmetry and function of StSurE.

Tensile behavior of a free-standing Pt-aluminide (PtAl) bond coat

The tensile behavior of a high activity stand-alone Pt-aluminide (PtAl) bond coat was evaluated by the micro-tensile test method at various temperatures (room temperature to 1100 degrees C) and strain rates (10(-5) s(-1)-10(-1) s(-1).) At all strain rates, the stress strain behavior of the stand-alone coating was significantly affected by the variation in temperature. The stress strain response was linear, indicating brittle behavior, at temperatures below the brittle ductile transition temperature (BDTT). The coating exhibited appreciable ductility (up to 2%) above the BDTT. The strength (both yield stress and ultimate tensile strength) of the coating decreased and its ductility increased with increasing temperature above the BDTT. The tensile behavior of the coating was sensitive to strain rate in the ductile regime, with its strength increasing with increasing strain rate at any given temperature. The BDTT of the coating was found to increase with increasing with increasing strain rate. The coating exhibited two distinct mechanisms of deformation above the BDTT. The transition temperature for the change of deformation mechanism also increased with increasing strain rate. (C) 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Study of the effect of alkali mixture on V-O bond length in Oxyfluoro Vanadate glasses using Raman spectroscopy

Raman spectroscopic study on Oxyfluoro Vanadate glasses containing various proportions of lithium fluoride and rubidium fluoride was carried out to see an effect of mixture of alkali on vanadium-oxygen (V-O) bond length. Glasses with a general formula 40V(2)O(5) - 30BaF(2) - (30 - x) LiF - xRbF (x = 0-30) were prepared. Room temperature Raman spectra of these glass samples were recorded in back scattering geometry. The data presented is in ``reduced Raman intensity'' form with maximum peak scaled to 100. We have used v = Aexp(BR), where A and B are fitting parameters, to correlate the bond length R with Raman scattering frequency v. We observed that variation in bond length and its distribution about a most probable value can be correlated to the alkali environment present in these glasses. We also observed that all rubidium environment around the network forming unit is more homogenous than all lithium environment.

Interstitial Defects Induced Ferroelectricity in Undoped ZnO Nanorods at Room Temperature

A simple approach for obtaining room temperature ferroelectricity in ZnO rod structures at the nanoscale is reported. A systematic comparative study between two kinds of nanorods prepared by different processes reveals the physics behind it. It is observed that ZnO nanorods grown (in-situ) by a sol gel method on platinum substrate show ferroelectric behaviour. On the contrary, ZnO nanorods first grown by a sol gel method and then spin-coated on a platinum substrate (ex-situ) do not demonstrate this kind of feature. X-ray diffraction analysis confirms partially (002) and (100) plane oriented growth of both samples. From photoluminescence (PL) spectral analysis it is interpreted that oxygen vacancies/zinc interstitial defects, which arises from the large lattice mismatch between the Pt substrate and the ZnO nanorods grown thereon, and preferential ZnO growth along 002], can be causes of this type of phenomena. C-V characterization, P-E hysteresis loop along with piezoelectric force microscopy support this observation.

Investigating thermal stability of structural defects and its effect on d(0) ferromagnetism in undoped SnO2

The effect of annealing on structural defects and d(0) ferromagnetism in SnO2 nanoparticles prepared by solution combustion method is investigated. The as-synthesized SnO2 nanoparticles were annealed at 400-800 degrees C for 2 h, in ambient conditions. The crystallinity, size, and morphology of the samples were studied using x-ray diffraction and transmission electron microscopy studies. The annealing results in grain growth due to coarsening as well as reduction in oxygen vacancies as confirmed by Raman spectroscopy, photoluminescence spectroscopy, and x-ray photoelectron spectroscopy. All the as synthesized and annealed samples exhibit room temperature ferromagnetism (RTFM) with distinct hysteresis loops and the saturation magnetization as high as similar to 0.02 emu/g in as-synthesized samples. However, the saturation magnetization is drastically reduced with increasing annealing temperature. Further the presence of singly charged oxygen vacancies (V-o(-) signal at g-value 1.99) is confirmed by electron paramagnetic resonance studies, which also diminish with increasing annealing temperature. The observed diminishing RTFM and simultaneous evidences of diminishing O vacancies clearly indicate that RTFM is driven by defects in oxide lattice and confirms primary role of oxygen vacancies in inducing ferromagnetic ordering in metal oxide semiconductors. The study also provides improved fundamental understanding regarding the ambiguity in the origin of intrinsic RTFM in semiconducting metal oxides and projects their technological application in the field of spintronics. (C) 2013 AIP Publishing LLC.