Stepwise Crystallization: Illustrative Examples of the Use of Metalloligands Cu-6(mna)(6)](6-) and (Ag-6(Hmna)(2)(mna)(4)](4-) (H(2)mna=2-Mercapto Nicotinic Acid) in the Formation of Heterometallic Two- and Three-Dimensional Assemblies with brucite, pcu, and sql Topologies

Three new inorganic coordination polymers, {Mn(H2O)(6)]-Mn-2(H2O)(6)](Cu-6(mna)(6)]center dot 6H(2)O}, 1, {Mn-4(OH)(2)(H2O)(10)] (Cu-6(mna)6]center dot 8H(2)O}, 2, and {Mn-2(H2O)(5)]Ag-6(Hmna)(2)(mna)(4)]center dot 20H(2)O}, 3, have been synthesized at room temperature through a sequential crystallization route. In addition, we have also prepared and characterized the molecular precursor Cu-6(Hmna)(6)]. Compounds 1 and 3 have a two-dimensional structure, whereas 2 has a three-dimensional structure. The formation of 2 has been achieved by minor modification in the synthetic composition, suggesting the subtle relationship between the reactant composition and the structure. The hexanudear copper and silver duster cores have Cu center dot center dot center dot Cu and Ag center dot center dot center dot Ag distances close to the sum of the van der Waals radii of Cu1+ and Ag1+, respectively. The connectivity between Cu-6(mna)(6)](6-) cluster units and Mn2+ ions gives rise to a brucite related layer in 1 and a pcu-net in 2. The Ag-6(Hmna)(2)(mna)(4)](4-) cluster in 3, on the other hand, forms a sql-net with Mn2+. Compound 1 exhibits an interesting and reversible hydrochromic behavior, changing from pale yellow to red, on heating at 70 degrees C or treatment under a vacuum. Electron paramagnetic resonance studies indicate no change in the valence states, suggesting the color change could be due to changes in the coordination environment only. The magnetic studies indicate weak antiferromagnetic behavior. Proton conductivity studies indicate moderate proton migrations in 1 and 3. The present study dearly establishes sequential crystallization as an important pathway for the synthesis of heterometallic coordination polymers.

Stable Crystalline Salts of Haloperidol: A Highly Water-Soluble Mesylate Salt

Haloperidol, an antipsychotic drug, was screened for new solid crystalline phases using high throughput crystallization in pursuit of solubility improvement. Due to the highly basic nature of the API, all the solid forms with acids were obtained in the form of salts. Eleven crystalline salts in the form of oxalate (1:1), benzoate (1:1), salicylate (1:1 and 1:2), 4-hydroxybenzoate (1:1), 4-hydroxybenzoate ethyl acetate solvate (1:1:1), 3,4-dihydroxybenzoate (1:1), 3,5-dihydroxybenzoate (1:1), mesylate (1:1), besylate (1:1), and tosylate (1:1) salt were achieved. There is an insertion of carboxylate or sulfonate anion into the hydrogen bonding pattern of haloperidol. The salts with the aliphatic carboxylic acids were found to be more prone to form salt hydrates compared with aromatic carboxylate salts. All the salts were subjected to solubility measurement in water at neutral pH. There was no direct correlation observed between the solubility of the salt and its coformer. All the salts are stable at room temperature as well as after 24 h slurry experiment except the oxalate salt, which showed an unusual phase transformation from its hydrated form to the anhydrous form. A structureproperty relationship was examined to analyze the solubility behavior of the solid forms.

Grain and the concomitant ferroelectric domain size dependent physical properties of Ba0.85Ca0.15Zr0.1Ti0.9O3 ceramics fabricated using powders derived from oxalate precursor route

Fine powders comprising nanocrystallites of Ba0.85Ca0.15Zr0.1Ti0.9O3 (BCZT) were synthesized via oxalate precursor method, which facilitated to obtain homogenous and large grain sized ceramics at a lower sintering temperature. The compacted powders were sintered at various temperatures in the range of 1200 degrees C-1500 degrees C for an optimized duration of 10 h. Interestingly the one that was sintered at 1450 degrees C/10 h exhibited well resolved Morphotrophic Phase Boundary. The average grain size associated with this sample was 30 mu m accompanied by higher domain density mostly with 90 degrees twinning. These were believed to have significant contribution towards obtaining large strain of about 0.2% and piezoelectric coefficient as high as 563 pC/N. The maximum force that was generated by BCZT ceramic (having 30 mu m grain size) was found to be 161 MPa, which is much higher than that of known actuator materials such as PZT (40MPa) and NKN-5-LT (7 MPa). (C) 2014 AIP Publishing LLC.

Phase relations in the system Ca-Ta-O and thermodynamics of calcium tantalates in relation to calciothermic reduction of Ta2O5

Phase equilibria of the system Ca-Ta-O is established by equilibrating eleven samples at 1200 K for prolonged periods and phase identification in quenched samples by optical and scanning electron microscopy, energy dispersive spectroscopy and X-ray diffraction. Four ternary oxides are identified: CaTa4O11, CaTa2O6, Ca2Ta2O7 and Ca4Ta2O9. Isothermal section of the phase diagram is composed using the results. Thermodynamic properties of the ternary oxides are measured in the temperature range from 975 to 1275 K employing solid-state galvanic cells incorporating single crystal CaF2 as the solid electrolyte. The cells essentially measure the chemical potentials of CaO in two-phase fields (Ta2O5 + CaTa4O11), (CaTa4O11 + CaTa2O6), (CaTa2O6 + Ca2Ta2O7), and (Ca2Ta2O7 + Ca4Ta2O9) of the pseudo-binary system CaO-Ta2O5. The standard Gibbs energies of formation of the four ternary oxides from their component binary oxides Ta2O5 and CaO are given by: Delta G(f)((ox))(o) (CaTa4O11) (+/- 482)/J mol(-1) = -58644+21.497 (T/K) Delta G(f)((ox))(o) (CaTa2O6) (+/- 618)/J mol(-1) = -55122+21.893 (T/K) Delta G(f)((ox))(o) (Ca2Ta2O7) (+/- 729)/J mol(-1) = -82562+31.843 (T/K) Delta G(f)((ox))(o) (Ca4Ta2O9) (+/- 955)/J mol(-1) = -126598+48.859 (T/K) The Gibbs energy of formation of the four ternary compounds obtained in this study differs significantly from that reported in the literature. The thermodynamic data and phase diagram are used for understanding the mechanism and kinetics of calciothermic and electrochemical reduction of Ta2O5 to metal. (C) 2014 Elsevier B.V. All rights reserved.

Calcium Permeable AMPA Receptor-Dependent Long Lasting Plasticity of Intrinsic Excitability in Fast Spiking Interneurons of the Dentate Gyrus Decreases Inhibition in the Granule Cell Layer

The local fast-spiking interneurons (FSINs) are considered to be crucial for the generation, maintenance, and modulation of neuronal network oscillations especially in the gamma frequency band. Gamma frequency oscillations have been associated with different aspects of behavior. But the prolonged effects of gamma frequency synaptic activity on the FSINs remain elusive. Using whole cell current clamp patch recordings, we observed a sustained decrease of intrinsic excitability in the FSINs of the dentate gyrus (DG) following repetitive stimulations of the mossy fibers at 30 Hz (gamma bursts). Surprisingly, the granule cells (GCs) did not express intrinsic plastic changes upon similar synaptic excitation of their apical dendritic inputs. Interestingly, pairing the gamma bursts with membrane hyperpolarization accentuated the plasticity in FSINs following the induction protocol, while the plasticity attenuated following gamma bursts paired with membrane depolarization. Paired pulse ratio measurement of the synaptic responses did not show significant changes during the experiments. However, the induction protocols were accompanied with postsynaptic calcium rise in FSINs. Interestingly, the maximum and the minimum increase occurred during gamma bursts with membrane hyperpolarization and depolarization respectively. Including a selective blocker of calcium-permeable AMPA receptors (CP-AMPARs) in the bath; significantly attenuated the calcium rise and blocked the membrane potential dependence of the calcium rise in the FSINs, suggesting their involvement in the observed phenomenon. Chelation of intracellular calcium, blocking HCN channel conductance or blocking CP-AMPARs during the experiment forbade the long lasting expression of the plasticity. Simultaneous dual patch recordings from FSINs and synaptically connected putative GCs confirmed the decreased inhibition in the GCs accompanying the decreased intrinsic excitability in the FSINs. Experimentally constrained network simulations using NEURON predicted increased spiking in the GC owing to decreased input resistance in the FSIN. We hypothesize that the selective plasticity in the FSINs induced by local network activity may serve to increase information throughput into the downstream hippocampal subfields besides providing neuroprotection to the FSINs. (c) 2014 Wiley Periodicals, Inc.

Individual and combined additions of calcium and antimony on microstructure and mechanical properties of squeeze-cast AZ91D magnesium alloy

The effects of combined additions of Ca and Sb on the microstructure and tensile properties of AZ91D alloy fabricated by squeeze-casting have been investigated. For comparison, the same has also been studied with and without individual additions of Ca and Sb. The results indicate that both individual and combined additions refine the grain size and beta-Mg17Al12 phase, which is more pronounced with combined additions. Besides alpha-Mg and beta-Mg17Al12 phases, a new reticular Al2Ca and rod-shaped Mg3Sb2 phases are formed following individual additions of Ca and Sb in the AZ91D alloy. With combined additions, an additional Ca2Sb phase is formed suppressing Mg3Sb2 phase. Additions of both Ca and Sb increase yield strength (YS) at both ambient and elevated temperatures up to 200 degrees C. However, both ductility and ultimate tensile strength (UTS) decrease first up to 150 degrees C and then increase at 200 degrees C. The increase in YS is attributed to the refinement of grain size, whereas, ductility and UTS are deteriorated by the presence of brittle Al2Ca, Mg3Sb2 and Ca2Sb phases. The best tensile properties are obtained in the AZXY9110 alloy owing to the presence of lesser amount of brittle Al2Ca and Ca2Sb phases resulted from the optimum content of 1.0Ca and 0.3Sb (wt%). The fracture surface of the tensile specimen tested at ambient temperature reveals cleavage failure that changes to quasi-cleavage at 200 degrees C. The squeeze-cast alloys exhibited better tensile properties as compared to that of the gravity-cast alloys nullifying the detrimental effects of Ca and/or Sb additions. (C) 2014 Elsevier B.V. All rights reserved.

Effect of solvent; enhancing the wettability and engineering the porous structure of a calcium phosphate/agarose composite for drug delivery

Tissue engineering deals with the regeneration of tissues for bone repair, wound healing, drug delivery, etc., and a highly porous 3D artificial scaffold is required to accommodate the cells and direct their growth. We prepared 3D porous calcium phosphate ((hydroxyapatite/beta-tricalcium phosphate)/agarose, (HAp/beta-TCP)/agarose) composite scaffolds by sol-gel technique with water (WBS) and ethanol (EBS) as solvents. The crystalline phases of HAp and beta-TCP in the scaffolds were confirmed by X-ray diffraction (XRD) analysis. The EBS had reduced crystallinity and crystallite size compared to WBS. WBS and EBS revealed interconnected pores of 1 mu m and 100 nm, respectively. The swelling ratio was higher for EBS in water and phosphate buffered saline (PBS). An in vitro drug loading/release experiment was carried out on the scaffolds using gentamicin sulphate (GS) and amoxicillin (AMX). We observed initial burst release followed by sustained release from WBS and EBS. In addition, GS showed more extended release than AMX from both the scaffolds. GS and AMX loaded scaffolds showed greater efficacy against Pseudomonas than Bacillus species. WBS exhibited enhanced mechanical properties, wettability, drug loading and haemocompatibility compared to EBS. In vitro cell studies showed that over the scaffolds, MC3T3 cells attached and proliferated and there was a significant increase in live MC3T3 cells. Both scaffolds supported MC3T3 proliferation and mineralization in the absence of osteogenic differentiation supplements in media which proves the scaffolds are osteoconducive. Microporous scaffolds (WBS) could assist the bone in-growth, whereas the presence of nanopores (EBS) could enhance the degradation process. Hence, WBS and EBS could be used as scaffolds for tissue engineering and drug delivery. This is a cost effective technique to produce scaffolds of degradable 3D ceramic-polymer composites.

Unique nanoporous antibacterial membranes derived through crystallization induced phase separation in PVDF/PMMA blends

In this study, a unique method was adopted to design porous membranes through crystallization induced phase separation in PVDF/PMMA (poly(vinylidene fluoride)/poly(methyl methacrylate)) blends. By etching out PMMA, which segregates either in the interlamellar and/or in the interspherulitic regions of the blends, nanoporous hierarchical structures can be derived. Different nanoparticles like titanium dioxide (TiO2), silver nanoparticle (Ag) decorated carbon nanotubes (Ag-CNTs), TiO2 decorated CNTs (TiO2-CNTs), Ag decorated TiO2 (Ag-TiO2) and Ag-TiO2 decorated CNTs (Ag@TiO2-CNTs) were synthesized and melt mixed with 80/20 PVDF/PMMA blends to render antibacterial activity to the membranes. Scanning electron microscopy (SEM) was used to study the crystalline morphology of the membranes. A significant improvement in the trans-membrane flux was obtained in the blends with Ag@TiO2 decorated CNTs as compared to the membranes derived from the neat blends, which can be attributed to the interconnected pores in these membranes. Both qualitative and quantitative studies of antifouling and antibacterial activity (using E. coli as a model bacterium) were performed using the standard plate count method. SEM micrographs clearly showed that the antifouling activity of the membranes was improved with addition of Ag@TiO2-CNTs. In the quantitative standard plate count method, the bacterial colony significantly decreased with the addition of Ag@TiO2-CNTs as against neat blends. This study opens a new avenue in the fabrication of polymer blend based membranes for water filtration.

Role of synergistic pi-pi stacking and X-H center dot center dot center dot Cl (X = C, N, O) H-bonding interactions in gelation and gel phase crystallization

The self-assembly of p-pyridyl-ended oligo-p-phenylenevinylenes (OPVs) in ethanol leads to the formation of either hollow or solid microrods. The corresponding protonated OPVs with n-butyl chains induce transparent gelation and also gel phase crystallization owing to various synergistic noncovalent interactions. The chloride ion-selective gelation, AIEE and stimuli responsiveness of the gel are also observed.

Phase stability of silver particles embedded calcium phosphate bioceramics

In this paper, we report the compositional variation-dependent phase stability of hydroxyapatite (Ca-10(PO4)(6)(OH)(2)) on doping with silver. The transformation of hydroxyapatite to (beta/alpha) tricalcium phosphate phases during sintering has been explored using Raman spectroscopy and X-ray diffraction techniques. The optical absorption spectroscopy analysis reveals the presence of Ag+ ions at low doping levels. As the doping increases, abundance of Ag particles is enhanced.

Piezoelectric properties of individual nanocrystallites of Ba0.85Ca0.15Zr0.1Ti0.9O3 obtained by oxalate precursor route

Nanocrystalline Ba0.85Ca0.15Zr0.1Ti0.9O3 (BCZT) powder was synthesized via the complex oxalate precursor route at a relatively low temperature (800 degrees C/5 h). The phase formation temperature of BCZT at nanoscale was confirmed by thermogravimetric (TG), differential thermal analysis (DTA) followed by X-ray powder diffraction (XRD) studies. Fourier transform infrared (FTIR) spectroscopy was carried out to confirm the complete decomposition of oxalate precursor into BCZT phase. The XRD and profile fitting revealed the coexistence of cubic and tetragonal phases and was corroborated by Raman study. Transmission electron microscopy (TEM) carried out on 800 degrees C and 1000 degrees C/5 h heat treated BCZT powder revealed the crystallite size to be in the range of 20-50 nm and 40-200 nm respectively. The optical band gap for BCZT nanocrystalline powder was obtained using Kubelka Munk function and was found to be around 3.12 +/- 0.02 eV and 3.03 +/- 0.02 eV respectively for 800 degrees C (20-50 nm) and 1000 degrees C/5 h (40-200 nm) heat treated samples. The piezoelectric properties were studied for two different crystallite sizes (30 and 70 nm) using a piezoresponse force microscope (PFM). The d(33) coefficients obtained for 30 nm and 70 nm sized crystallites were 4 pm V-1 and 47 pm V-1 respectively. These were superior to that of BaTiO3 nanocrystal (approximate to 50 nm) and promising from a technological/industrial applications viewpoint.

Calcium binding properties of calcium dependent protein kinase 1 (CaCDPK1) from Cicer arietinum

Calcium plays a crucial role as a secondary messenger in all aspects of plant growth, development and survival. Calcium dependent protein kinases (CDPKs) are the major calcium decoders, which couple the changes in calcium level to an appropriate physiological response. The mechanism by which calcium regulates CDPK protein is not well understood. In this study, we investigated the interactions of Ca2+ ions with the CDPK1 isoform of Cicer arietinum (CaCDPK1) using a combination of biophysical tools. CaCDPK1 has four different EF hands as predicted by protein sequence analysis. The fluorescence emission spectrum of CaCDPK1 showed quenching with a 5 nm red shift upon addition of calcium, indicating conformational changes in the tertiary structure. The plot of changes in intensity against calcium concentrations showed a biphasic curve with binding constants of 1.29 mu M and 120 mu M indicating two kinds of binding sites. Isothermal calorimetric (ITC) titration with CaCl2 also showed a biphasic curve with two binding constants of 0.027 mu M and 1.7 mu M. Circular dichroism (CD) spectra showed two prominent peaks at 208 and 222 nm indicating that CaCDPK1 is a alpha-helical rich protein. Calcium binding further increased the alpha-helical content of CaCDPK1 from 75 to 81%. Addition of calcium to CaCDPK1 also increased fluorescence of 8-anilinonaphthalene-1-sulfonic acid (ANS) indicating exposure of hydrophobic surfaces. Thus, on the whole this study provides evidence for calcium induced conformational changes, exposure of hydrophobic surfaces and heterogeneity of EF hands in CaCDPK1. (C) 2015 Elsevier GmbH. All rights reserved.

Twinning induced enhancement of fracture toughness in ultrafine grained Hydroxyapatite-Calcium Titanate composites

Despite being highly bioactive and biocompatible, the limitations of monolithic hydroxyapatite (HA) include extremely low fracture toughness, poor electrical conductivity. While addressing these issues, the present study demonstrates how CaTiO3 (CT) addition to HA can be utilized to obtain a combination of long crack fracture toughness (1.7 MPa m(1/2) SEVNB technique) and flexural strength of 98-155 MPa (3-point bending) and a moderate tensile strength (diametral compression) of 17-36 MPa. The enhancement in fracture resistance in spark plasma sintered HA-CT composites has been explained in reference to the observed twin morphology. TEM reveals the presence of twins in CT grains due to 1800 rotation about 101]. The measured properties along with our earlier reports on biocompatibility and electrical properties make HA-CT suitable for bone tissue engineering applications. When compared with other competing HA-based biocomposites, HA-CT composites are found to have a better combination of properties useful for medium load bearing implant applications. (C) 2015 Elsevier Ltd. All rights reserved.

Structural Evolution and Property Changes in Nd_{60}Al_{10}Fe_{20}Co_{10} Bulk Metallic Glass During Crystallization

The structural evolution and property changes in Nd60Al10Fe20Co10 bulk metallic glass (BMG) upon crystallization are investigated by the ultrasonic method, x-ray diffraction, density measurement, and differential scanning calorimetry. The elastic constants and Debye temperature of the BMG are obtained as a function of annealing temperature. Anomalous changes in ultrasonic velocities, elastic constants, and density are observed between 600–750 K, corresponding to the formation of metastable phases as an intermediate product in the crystallization process. The changes in acoustic velocities, elastic constants, density, and Debye temperature of the BMG relative to its fully crystallized state are much smaller, compared with those of other known BMGs, the differences being attributed to the microstructural feature of the BMG.

Effects of the orientation of microgravity on the concentration distribution in crystallization from solution

A quasi-steady state growth and dissolution in a 2-D rectangular enclosure is numerically investigated. This paper is an extension to indicate the effects of the orientation of gravity on the concentration field in crystallization from solution under microgravity, especially on the lateral non-uniformity of concentration distribution at the growth surface. The thermal and solute convection are included in this model.