Gibbs energy of formation of lead zirconate

The Gibbs energy of formation of zirconia-saturated lead zirconate was determined by emf measurements on the solid state cells and at 800 to 1400 K. The results obtained differ significantly from those reported in the literature based on vapor-pressure measurements, using Knudsen effusion and transportation techniques and assuming that the vapor phase consisted entirely of monomeric PbO molecules. A reanalysis of the data obtained in the earlier vapor-pressure studies, using mass-spectrometric measurements on polymeric PbO species in the gas phase, gives Gibbs energies of formation of lead zirconate which are in better agreement with those obtained in this study. Recent electrochemical measurements using CaO-ZrO2 and PbF2 solid electrolytes are in good agreement with the present study. The results obtained in this study are also consistent with the phase diagram which shows decomposition of the zirconate to tetragonal zirconia and a liquid phase rich in PbO at 1843 K.

Activity of TiO2 in the System ZrO2-TiO2 and Gibbs Energy of Formation of ZrTiO4

The activity of Ti02 in single and two··phase regions of ihe system ZrOrTi02 has heen measured lIsing solid state cells based on yttria··doped tho ria (YDT) as the solid electrolyte at 1373 K. The cells used can be represented as: Pt, Tio.07PtO.Y3 + Zrj.,Tix0 2 / YDT / Ti02 + Tio.07Pto.93, Pt Pt, Tio.07Pto.93 + ZrJ.xTix02 + ZrTi04 / YDT / Ti02+ Tio.07PtO.93, Pt In each cell the composition of Pt-Ti alloy was identical at hoth electrodes. The emf of the cell is therefore directly related to the activity of Ti02 in oxide phase or oxide phase mixture: aTiO~ :;: cxp (-4FE/RT). The activity coefficient of Ti02 in th~ zirconia-rich solid solution with monoclinic structure (CUl2 2" XTi02 2" 0) can be expressed as:In the zirconia-rich solid solution with tetragonal structure (0.085 2" X ri02 2" 0.03), the activity coefficient is given by:In YTi02 (± 0.012) = 2.354 (1-XTiO? )2 +0.064 The standard Gibbs energy of formation of ZrTi04 is -5650 (± 200) J/mol at 1373 K .

Thermodynamic activities in the Pb(Zr1−XTiX)O3 solid solution at 1373K

Although Pb(Zr1−XTiX)O3 solid solution is the cornerstone of the piezoelectric ceramics, there is no information in the literature on thermodynamic activities of the component phases in the solid solution. Using inter-crystalline ion exchange equilibria between Pb(Zr1−XTiX)O3 solid solution with cubic perovskite structure and (Zr1−YTiY)O2 solid solutions with monoclinic and tetragonal structures, activities of PbTiO3 and PbZrO3 in the perovskite solid solution have been derived at 1373 K using the modified Gibbs–Duhem integration technique of Jacob and Jeffes. Tie-lines from the cubic solid solution are skewed towards the ZrO2 corner. Activities in the zirconia-rich (Zr1−YTiY)O2 solid solutions are taken from a recent emf study. The results for the perovskite solid solution at 1373 K can be represented by a sub-regular solution model:View the MathML sourcewhere ΔGE,M is the excess Gibbs energy of mixing of the cubic solid solution and Xi represents the mole fraction of component i. There is a significant positive deviation from ideality for PbTiO3-rich compositions and mild negative deviation near the PbZrO3 corner. The cubic solid solution is intrinsically stable against composition fluctuations at temperatures down to 840 K. The results contrast sharply with the recent calorimetric data on enthalpy of mixing which signal instability of the cubic perovskite solid solution.

Phenylboronic acids in crystal engineering: Utility of the energetically unfavorable syn,syn-conformation in co-crystal design

Phenylboronic acids can exist, in principle, in three different conformers (syn,syn; syn,anti and anti,anti) with distinct energy profiles. In their native state, these compounds prefer the energetically favored syn, anti-conformation. In molecular complexes, however, the functionality exhibits conformational diversity. In this paper we report a series of co-crystals, with N-donor compounds, prepared by a design strategy involving the synthons based on the syn, syn-conformation of the boronic acid functionality. For this purpose, we employed compounds with the 1,2-diazo fragment (alprazolam, 1H-tetrazole, acetazolamide and benzotriazole), 1,10-phenanthroline and 2,2'-bipyridine for the co-crystallization experiments. However, our study shows that the mere presence of the 1,2-diazo fragment in the coformer does not guarantee the successful formation of co-crystals with a syn, syn-conformation of the boronic acid. [GRAPHICS] The -B(OH)(2) fragment makes unsymmetrical O-H center dot center dot center dot N heterosynthons with alprazolam (ALP) and 1,10-phenanthroline (PHEN). In the co-crystals of phenylboronic acids with 1H-tetrazole (TETR) and 2,2'-bipyridine (BPY), the symmetrical boronic acid dimer is the major synthon. In the BPY complex, boronic acid forms linear chains and the pyridine compound interacts with the lateral OH of boronic acid dimers that acts as a connector, thus forming a ladder structure. In the TETR complex, each heterocycle interacts with three boronic acids. While two boronic acids interact using the phenolic group, the third molecule generates O-H center dot center dot center dot N hydrogen bonds using the extra OH group, of -B(OH)(2) fragment, left after the dimer formation. Thus, although molecules were selected retrosynthetically with the 1,2-diazo fragment or with nearby hetero-atoms to induce co-crystal formation using the syn,syn-orientation of the -B(OH)(2) functionality, co-crystal formation is in fact selective and is probably driven by energy factors. Acetazolamide (ACET) contains self-complementary functional groups and hence creates stable homosynthons. Phenylboronic acids being weak competitors fail to perturb the homosynthons and hence the components crystallize separately. Therefore, besides the availability of possible hydrogen bond acceptors in the required position and orientation, the ability of the phenyl-boronic acid to perturb the existing interactions is also a prerequisite to form co-crystals. This is illustrated in the table below. In the case of ALP, PHEN and BPY, the native structures are stabilized by weak interactions and may be influenced by the boronic acid fragment. Thus phenylboronic acids can attain co-crystals with those compounds, wherein the cyclic O-H center dot center dot center dot N hydrogen bonds are stronger than the individual homo-interactions. This can lower the lattice energy of the molecular complex as compared with the individual crystals. [GRAPHICS] Phenylboronic acids show some selectivity in the formation of co-crystals with N-heterocycles. The differences in solubility of the components fall short to provide a possible reason for the selective formation of co-crystals only with certain compounds. These compounds, being weak acids, do not follow the Delta pK(a) analysis and hence fail to provide any conclusive observation. Theoretical results show that of the three conformers possible, the syn,anti conformer is the most stable. The relative stabilities of the three conformers syn,anti,syn,syn and anti,anti are 0.0, 2.18 and 3.14 kcal/mol, respectively. The theoretical calculations corroborate the fact that only energetically favorable synthons can induce the formation of heterosynthons, as in ALP and PHEN complexes. From a theoretical and structural analysis it is seen that phenylboronic acids will form interactions with those molecules wherein the heterocyclic and acidic fragments can interrupt the homosynthons. However, the energy profile is shallow and can be perturbed easily by the presence of competing functional groups (such as OH and COOH) in the vicinity. [GRAPHICS] .

Role of Nonplanar Peptide Unit in Regular Polypeptide Helices - New Model for Pply-Beta-Benzyl-L-Aspartate

The effect of non-planarity of the peptide unit on helical structures stabilized by intrachain hydrogen bonds is discussed. While the present calculations generally agree with those already reported in the literature for right-handed helical structures, it is found that the most stable left-handed structure is a novel helix, called the delta-helix. Its helical parameters are close to these reported for poly-beta-benzyl-L -aspartate. Conformational energy calculations show that poly-beta-benzyl-L -aspartate with the delta-helical structure is considerably more stable than the structure it is generally believed to take up (the omega-helix) by about 15 kcal/mol-residue.

Smooth DMS-FEM: A new approach to solving nearly incompressible nonlinear elasto-static problems

The DMS-FEM, which enables functional approximations with C(1) or still higher inter-element continuity within an FEM-based meshing of the domain, has recently been proposed by Sunilkumar and Roy [39,40]. Through numerical explorations on linear elasto-static problems, the method was found to have conspicuously superior convergence characteristics as well as higher numerical stability against locking. These observations motivate the present study, which aims at extending and exploring the DMS-FEM to (geometrically) nonlinear elasto-static problems of interest in solid mechanics and assessing its numerical performance vis-a-vis the FEM. In particular, the DMS-FEM is shown to vastly outperform the FEM (presently implemented through the commercial software ANSYS (R)) as the former requires fewer linearization and load steps to achieve convergence. In addition, in the context of nearly incompressible nonlinear systems prone to volumetric locking and with no special numerical artefacts (e.g. stabilized or mixed weak forms) employed to arrest locking, the DMS-FEM is shown to approach the incompressibility limit much more closely and with significantly fewer iterations than the FEM. The numerical findings are suggestive of the important role that higher order (uniform) continuity of the approximated field variables play in overcoming volumetric locking and the great promise that the method holds for a range of other numerically ill-conditioned problems of interest in computational structural mechanics. (C) 2011 Elsevier Ltd. All rights reserved.

Triclabendazole: An Intriguing Case of Co-existence of Conformational and Tautomeric Polymorphism

The crystal polymorphism of the anthelmintic drug, triclabendazole (TCB), is described. Two anhydrates (Forms I and II), three solvates, and an amorphous form have been previously mentioned. This study reports the crystal structures of Forms I (1) and II (2). These structures illustrate the uncommon phenomenon of tautomeric polymorphism. TCB exists as two tautomers A and B. Form I (Z'=2) is composed of two molecules of tautomer A while Form II (Z'=1) contains a 1:1 mixture of A and B. The polymorphs are also characterized by using other solid-state techniques (differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), PXRD, FT-IR, and NMR spectroscopy). Form I is the higher melting form (m.p.: 177 degrees C, Delta Hf=approximate to 105 +/- 4 Jg-1) and is the more stable form at room temperature. Form II is the lower melting polymorph (m.p.: 166 degrees C, Delta Hf=approximate to 86 +/- 3 Jg-1) and shows high kinetic stability on storage in comparison to the amorphous form but it transforms readily into Form I in a solution-mediated process. Crystal structure analysis of co-crystals 3-11 further confirms the existence of tautomeric polymorphism in TCB. In 3 and 11, tautomer A is present whereas in 4-10 the TCB molecule exists wholly as tautomer B. The DFT calculations suggest that the optimized tautomers A and B have nearly the same energies. Single point energy calculations reveal that tautomer A (in Form I) exists in two low-energy conformations, whereas in Form II both tautomers A and B exist in an unfavorable high-energy conformation, stabilized by a five-point dimer synthon. The structural and thermodynamic features of 1-11 are discussed in detail. Triclabendazole is an intriguing case in which tautomeric and conformational variations co-exist in the polymorphs.

Chain Length Effects on Helix-Hairpin Distribution in Short Peptides with Aib-(D)Ala and Aib-Aib Segments

The Aib-(D)Ala dipeptide segment has a tendency to form both type-I'/III' and type-I/III beta-turns. The occurrence of prime turns facilitates the formation of beta-hairpin conformations, while type-I/III turns can nucleate helix formation. The octapeptide Boc-Leu-Phe-Val-Aib-(D)Ala-Leu-Phe-Val-OMe (1) has been previously shown to form a beta-hairpin in the crystalline state and in solution. The effects of sequence truncation have been examined using the model peptides Boc-Phe-Val-Aib-Xxx-Leu-Phe-NHMe (2, 6), Boc-Val-Aib-Xxx-Leu-NHMe (3, 7), and Boc-Aib-Xxx-NHMe (4, 8), where Xxx = (D)Ala, Aib. For peptides with central Aib-Aib segments, Boc-Phe-Val-Aib-Aib-Leu-Phe-NHMe (6), Boc-Val-Aib-Aib-Leu-NHMe (7), and Boc-Aib-Aib-NHMe (8) helical conformations have been established by NMR studies in both hydrogen bonding (CD(3)OH) and non-hydrogen bonding (CDCl(3)) solvents. In contrast, the corresponding hexapeptide Boc-Phe-Val-Aib-(D)Ala-Leu-Phe-Val-NHMe (2) favors helical conformations in CDCl(3) and beta-hairpin conformations in CD(3)OH. The beta-turn conformations (type-I'/III) stabilized by intramolecular 4 -> 1 hydrogen bonds are observed for the peptide Boc-Aib-(D)Ala-NHMe (4) and Boc-Aib-Aib-NIiMe (8) in crystals. The tetrapeptide Boc-Val-Aib-Aib-Leu-NHMe (7) adopts an incipient 3(10)-helical conformation stabilized by three 4 -> 1 hydrogen bonds. The peptide Boc-Val-Aib-(D)Ala-Leu-NHMe (3) adopts a novel et-turn conformation, stabilized by three intramolecular hydrogen bonds (two 4 -> 1 and one 5 -> 1). The Aib-L(D)Ala segment adopts a type-I' beta-turn conformation. The observation of an NOE between Val (1) NH <-> HNCH(3) (5) in CD(3)OH suggests, that the solid state conformation is maintained in methanol solutions. (C) 2011 Wiley Periodicals, Inc. Biopolymers (Pept Sci) 96: 744-756, 2011.

Monodispersity and stability: case of ultrafine aluminium nanoparticles (< 5 nm) synthesized by the solvated metal atom dispersion approach

The synthesis of THF coordinated aluminium nanoparticles by the solvated metal atom dispersion (SMAD) method is described. These colloids are not stable with respect to precipitation of aluminium nanoparticles. The precipitated aluminium nanopowder is highly pyrophoric. Highly monodisperse colloidal aluminium nanoparticles (3.1 +/- 0.6 nm) stabilized by a capping agent, hexadecyl amine (HDA), have also been prepared by the SMAD method. They are stable towards precipitation of particles for more than a week. The Al-HDA nanoparticles are not as pyrophoric as the Al-THF samples. Particles synthesized in this manner were characterized by high-resolution electron microscopy and powder X-ray diffraction. Annealing of the Al-HDA nanoparticles resulted in carbonization of the capping agent on the surface of the particles which imparts air stability to them. Carbonization of the capping agent was established using Raman spectroscopy and TEM. The annealed aluminium nanoparticles were found to be stable even upon their exposure to air for over a month which was evident from the powder XRD, TGA/DSC, and TEM studies. The successful passivation was further confirmed with the determination of high active aluminium content (95 wt%) upon exposure and storage under air.

Nitrates-melt synthesized LiNi0.8Co0.2O2 and its performance as cathode in Li-ion cells

Layered LiNi0.8Co0.2O2 crystallizing in R (3) over barm space group is synthesized by decomposing the constituent metal-nitrate precursors. Oxidizing nature of metal nitrates stabilizes nickel in +3 oxidation state, enabling a high degree of cation ordering in the layered LiNi0.8Co0.2O2. The powder sample characterized by XRD Rietveld refinement reveals <2% Li-Ni site exchange in the layers. Scanning electron microscopic studies on the as-synthesized LiNi0.8Co0.2O2 sample reflect well defined particles of cubic morphology with particle size ranging between 200 and 250 nm. Cyclic voltammograms suggest that LiNi0.8Co0.2O2 undergoes phase transformation on first charge with resultant phase being completely reversible in subsequent cycles. The first-charge-cycle phase transition is further supported by impedance spectroscopy that shows substantial reduction in resistance during initial de-intercalation. Galvanostatic charge-discharge cycles reflect a first-discharge capacity of 184 mAh g(-1) which is stabilized at 170 mAh g(-1) over 50 cycles.

One step synthesis of monoclinic VO2 (B) bundles of nanorods: Cathode for Li ion battery

One of the metastable phases of vanadium dioxide, VO2(B) bundles of nanorods and microspheres have been synthesized through a simple hydrothermal method by dispersing V2O5 in aqueous quinol. The obtained products were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and electrochemical discharge-charge test for lithium battery. It was found that the morphologies of the obtained VO2(B) can be tuned by manipulating the relative amount of quinol. The electrochemical test found that the bundles of nanorods exhibit an initial discharge capacity of 171 mAh g(-1) and its almost stabilized capacity was reached to 108 mAh g(-1) after 47 cycles at a current density of 0.1 mA g(-1). The formation mechanism of the VO2(B) bundles of nanorods and microspheres was also discussed. (C) 2012 Elsevier Inc. All rights reserved.

Insights into the Fold Organization of TIM Barrel from Interaction Energy Based Structure Networks

There are many well-known examples of proteins with low sequence similarity, adopting the same structural fold. This aspect of sequence-structure relationship has been extensively studied both experimentally and theoretically, however with limited success. Most of the studies consider remote homology or ``sequence conservation'' as the basis for their understanding. Recently ``interaction energy'' based network formalism (Protein Energy Networks (PENs)) was developed to understand the determinants of protein structures. In this paper we have used these PENs to investigate the common non-covalent interactions and their collective features which stabilize the TIM barrel fold. We have also developed a method of aligning PENs in order to understand the spatial conservation of interactions in the fold. We have identified key common interactions responsible for the conservation of the TIM fold, despite high sequence dissimilarity. For instance, the central beta barrel of the TIM fold is stabilized by long-range high energy electrostatic interactions and low-energy contiguous vdW interactions in certain families. The other interfaces like the helix-sheet or the helix-helix seem to be devoid of any high energy conserved interactions. Conserved interactions in the loop regions around the catalytic site of the TIM fold have also been identified, pointing out their significance in both structural and functional evolution. Based on these investigations, we have developed a novel network based phylogenetic analysis for remote homologues, which can perform better than sequence based phylogeny. Such an analysis is more meaningful from both structural and functional evolutionary perspective. We believe that the information obtained through the ``interaction conservation'' viewpoint and the subsequently developed method of structure network alignment, can shed new light in the fields of fold organization and de novo computational protein design.

Vanadium pentoxide nanobelts: One pot synthesis and its lithium storage behavior

In this paper, we report a synthesis, characterization and electrochemical properties of V2O5 nanobelts. V2O5 nanobelts have been prepared via hydrothermal treatment of commercial V2O5 in acidic (HCl/H2SO4) medium at relatively low temperature (160 degrees C). The hydrothermally derived products have been characterized by powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, X-ray photo electron spectroscopy (XPS), UV-Vis spectroscopy, Scanning/Transmission electron microscopy (SEM/TEM). XRD pattern of V2O5 nanobelts show an orthorhombic phase. From the FTIR spectrum, the peak observed at 1018 cm-1 is characteristic of the stretching vibration mode of the terminal vanadyl, V = O. The UV-Vis absorption spectrum of V2O5 nanobelts show maximum absorbance at 430 nm, which was blue-shifted compared to that of bulk V2O5. TEM micrographs reveal that the products consist of nanobelts of 40-200 nm in thickness and several tens of micrometers in length. The electrochemical analysis shows an initial discharge capacity of 360 mAh g-1 and its almost stabilized capacity is reached to 250 mAh g-1 after 55 cycles. A probable reaction mechanism for the formation of orthorhombic V2O5 nanobelts is proposed.

Nanoindentation as a probe for mechanically-induced molecular migration in layered organic donor-acceptor complexes

Nanoindentation and scratch experiments on 1:1 donor-acceptor complexes, 1 and 2, of 1,2,4,5-tetracyanobenzene with pyrene and phenanthrene, respectively, reveal long-range molecular layer gliding and large interaction anisotropy. Due to the layered arrangements in these crystals, these experiments that apply stress in particular directions result in the breaking of interlayer interactions, thus allowing molecular sheets to glide over one another with ease. Complex 1 has a layered crystal packing wherein the layers are 68° skew under the (002) face and the interlayer space is stabilized by van der Waals interactions. Upon indenting this surface with a Berkovich tip, pile-up of material was observed on just one side of the indenter due to the close angular alignment of the layers with the half angle of the indenter tip (65.35°). The interfacial differences in the elastic modulus (21 ) and hardness (16 ) demonstrate the anisotropic nature of crystal packing. In 2, the molecular stacks are arranged in a staggered manner; there is no layer arrangement, and the interlayer stabilization involves C-H�N hydrogen bonds and ��� interactions. This results in a higher modulus (20 ) for (020) as compared to (001), although the anisotropy in hardness is minimal (4 ). The anisotropy within a face was analyzed using AFM image scans and the coefficient of friction of four orthogonal nanoscratches on the cleavage planes of 1 and 2. A higher friction coefficient was obtained for 2 as compared to 1 even in the cleavage direction due to the presence of hydrogen bonds in the interlayer region making the tip movement more hindered. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Growth of Polypyrrole-Horseradish Peroxidase Microstructures for H2O2 Biosensor

Conducting polymer microstructures for enzymatic biosensors are developed by a facile electrochemical route. Horseradish peroxide (HRP)-entrapped polypyrrole (PPy) films with bowl-shaped microstructures are developed on stainless steel (SS 304) substrates by a single-step process. Potentiodynamic scanning/cyclic voltammetry is used for generation of PPy microstructures using electrogenerated oxygen bubbles stabilized by zwitterionic surfactant/buffer N-2-hydroxyethylpiperazine N-2-ethanesulfonic acid as soft templates. Scanning electron microscopic images reveal the bowl-shaped structures surrounded by cauliflower-like fractal PPy films and globular nanostructures. Raman spectroscopy reveals the oxidized nature of the film. Sensing properties of PPy-HRP films for hydrogen peroxide (H2O2) are demonstrated. Electrochemical characterization of the sensor films is done by linear sweep voltammetry (LSV) and amperometry. LSV results indicated the reduction of H2O2 and linearity in response of the sensing film. The amperometric biosensor has a performance comparable to those in the literature with advantages of hard-template free synthesis procedure and a satisfactory sensitivity value of 12.8 mu A/(cm(2) . mM) in the range of 1-10 mM H2O2.