Sensitive Liquid Chromatography-Tandem Mass Spectrometry Method for the Determination of Olanzapine in Human Urine

A sensitive and selective liquid chromatographic-tandem mass spectrometric (LC-MS-MS) method was developed to determine olanzapine (OLZ) in human urine. After solid-phase extraction with SPE cartridge, the urine sample was analysed on a C-18 column (Symmetry 3.5 mu m, 50 x 4.6 mm i.d) interfaced with a triple quadrupole tandem mass spectrometer. Positive electrospray ionization was employed as the ionization source. The mobile phase consisted of ammonium acetate (pH 7.8)-acetonitrile (10:90, v/v). The method was linear over a concentration range of 1-100 ngml(-1). The lower limit of quantitation was 1 ngml(-1). The intra-day and inter-day relative standard deviation across three validation runs over the entire concentration range was < 11.5 %. The accuracy determined at three concentrations (8.0, 50.0 and 85.0 ngml(-1) OLZ) was within +/- 1.21 % in terms of relative errors.

High-pressure synchrotron x-ray diffraction study of RMnO3 (R=Eu, Gd, Tb and Dy) upto 50 GPa

We have carried out synchrotron based high-pressure x-ray diffraction study of orthorhombic EuMnO3, GdMnO3, TbMnO3 and DyMnO3 up to 54.4, 41.6, 47.0 and 50.2 GPa, respectively. The diffraction peaks of all the four manganites shift monotonically to higher diffraction angles and the crystals retain the orthorhombic structure till the highest pressure. We have fitted the observed volume versus pressure data with the Birch-Murnaghan equation of state and determined the bulk modulus to be 185 +/- 6 GPa, 190 +/- 16 GPa, 188 +/- 9 GPa and 192 +/- 8 GPa for EuMnO3, GdMnO3, TbMnO3 and DyMnO3, respectively. The bulk modulus of EuMnO3 is comparable to other manganites, in contrast to theoretical predictions.

High-temperature, high-pressure granulites (retrogressed eclogites) in the central region of the Lewisian, NW Scotland: Crustal-scale subduction in the Neoarchaean

Eclogites and associated high-pressure (HP) rocks in collisional and accretionary orogenic belts preserve a record of subduction and exhumation, and provide a key constraint on the tectonic evolution of the continents. Most eclogites that formed at high pressures but low temperatures at > 10-11 kbar and 450-650 degrees C can be interpreted as a result of subduction of cold oceanic lithosphere. A new class of high-temperature (HT) eclogites that formed above 900 degrees C and at 14 to 30 kbar occurs in the deep continental crust, but their geodynamic significance and processes of formation are poorly understood. Here we show that Neoarchaean mafic-ultramafic complexes in the central granulite facies region of the Lewisian in NW Scotland contain HP/HT garnet-bearing granulites (retrogressed eclogites), gabbros, Iherzolites, and websterites, and that the HP granulites have garnets that contain inclusions of omphacite. From thermodynamic modeling and compositional isopleths we calculate that peak eclogite-facies metamorphism took place at 24-22 kbar and 1060-1040 degrees C. The geochemical signature of one (G-21) of the samples shows a strong depletion of Eu indicating magma fractionation at a crustal level. The Sm-Nd isochron ages of HP phases record different cooling ages of ca. 2480 and 2330 Ma. We suggest that the layered mafic-ultramafic complexes, which may have formed in an oceanic environment, were subducted to eclogite depths, and exhumed as HP garnet-bearing orogenic peridotites. The layered complexes were engulfed by widespread orthogneisses of tonalite-trondhjemite-granodiorite (TTG) composition with granulite facies assemblages. We propose two possible tectonic models: (1) the fact that the relicts of eclogitic complexes are so widespread in the Scourian can be taken as evidence that a >90 km x 40 km-size slab of continental crust containing mafic-ultramafic complexes was subducted to at least 70 km depth in the late Archaean. During exhumation the gneiss protoliths were retrogressed to granulite facies assemblages, but the mafic-ultramafic rocks resisted retrogression. (2) The layered complexes of mafic and ultramafic rocks were subducted to eclogite-facies depths and during exhumation under crustal conditions they were intruded by the orthogneiss protoliths (TTG) that were metamorphosed in the granulite facies. Apart from poorly defined UHP metamorphic rocks in Norway, the retrogressed eclogites in the central granulite/retrogressed eclogite facies Lewisian region, NW Scotland have the highest crustal pressures so far reported for Archaean rocks, and demonstrate that lithospheric subduction was transporting crustal rocks to HP depths in the Neoarchaean. (C) 2012 International Association for Gondwana Research. Published by Elsevier B.V. All rights reserved.

Evolution of microhardness and microstructure in a cast Al–7 % Si alloy during high-pressure torsion

Disks of a cast Al-7 % Si alloy were processed through high-pressure torsion (HPT) for 1/4, 1/2, 1, 5, and 10 revolutions under a pressure of 6.0 GPa and at temperatures of 298 and 445 K. The hardness of the samples after processing was significantly higher than in the cast sample, and the hardness profiles across the samples became more uniform with increasing numbers of turns. Processing at higher temperature gave lower hardness values. Experiments were conducted to examine the effects of HPT processing on various microstructural aspects of the cast Al-7 % Si alloy such as the grain size, the Taylor factor, and the fraction of high-angle grain boundaries. The results demonstrate that there is a correlation between trends in the microhardness values and the observed microstructures.

A structural and spectroscopic investigation of reduced graphene oxide under high pressure

The effect of high pressure on reduced graphene oxide (RGO) has been investigated using X-ray diffraction (XRD) and infrared (IR) absorption spectroscopy. Our XRD measurements show two-step reversible compression in the inter-layer spacing of RGO whereas intra-layer ordering exhibits a high pressure behavior similar to that of graphite up to 20 GPa. The line shape analysis of (100) peak, representing the intra-layer ordering, suggests presence of local out of plane distortions in RGO in the form of puckered regions which progressively straighten out as a function of pressure. IR measurements show reversible changes in spectroscopic features attributed to remnant functional groups in the inter-layer region. These measurements suggest high stability and recovering ability of RGO under pressure cycling. (C) 2014 Elsevier Ltd. All rights reserved.

A molecular dynamics study of ambient and high pressure phases of silica: Structure and enthalpy variation with molar volume

Extensive molecular dynamics studies of 13 different silica polymorphs are reported in the isothermal-isobaric ensemble with the Parrinello-Rahman variable shape simulation cell. The van Beest-Kramer-van Santen (BKS) potential is shown to predict lattice parameters for most phases within 2%-3% accuracy, as well as the relative stabilities of different polymorphs in agreement with experiment. Enthalpies of high-density polymorphs - CaCl2-type, alpha-PbO2-type, and pyrite-type for which no experimental data are available as yet, are predicted here. Further, the calculated enthalpies exhibit two distinct regimes as a function of molar volume-for low and medium-density polymorphs, it is almost independent of volume, while for high-pressure phases a steep dependence is seen. A detailed analysis indicates that the increased short-range contributions to enthalpy in the high-density phases arise not only from an increased coordination number of silicon but also shorter Si-O bond lengths. Our results indicate that amorphous phases of silica exhibit better optimization of short-range interactions than crystalline phases at the same density while the magnitude of Coulombic contributions is lower in the amorphous phase. (C) 2014 AIP Publishing LLC.

Effect of High-Pressure Torsion on Texture, Microstructure, and Raman Spectroscopy: Case Study of Fe- and Te-Substituted CoSb3

Fe0.05Co0.95Sb2.875Te0.125, a double-element-substituted skutterudite, was prepared by induction melting, annealing, and hot pressing (HP). The hot-pressed sample was subjected to high-pressure torsion (HPT) with 4 GPa pressure at 673 K. X-ray diffraction was performed before and after HPT processing of the sample; the skutterudite phase was observed as a main phase, but an additional impurity phase (CoSb2) was observed in the HPT-processed sample. Surface morphology was determined by high-resolution scanning electron microscopy. In the HP sample, coarse grains with sizes in the range of approximately 100 nm to 300 nm were obtained. They changed to fine grains with a reduction in grain size to 75 nm to 125 nm after HPT due to severe plastic deformation. Crystallographic texture, as measured by x-ray diffraction, indicated strengthening of (112), (102) poles and weakening of the (123) pole of the HPT-processed sample. Raman-active vibrational modes showed a peak position shift towards the lower energy side, indicating softening of the modes after HPT. The distortion of the rectangular Sb-Sb rings leads to broadening of Sb-Sb vibrational modes due to local strain fluctuation. In the HPT process, a significant effect on the shorter Sb-Sb bond was observed as compared with the longer Sb-Sb bond.

High pressure studies on the electrical resistivity of Ge-Te-Tl glasses

The variation of electrical resistivity in the system of glasses Ge17Te83-xTlx, with (1 <= x <= 13), has been studied as a function of high pressure for pressures up to 10 GPa. It is found that the normalized electrical resistivity decreases continuously with the increase in pressure and shows a sudden drop at a particular pressure (transition pressure), indicating the presence of a transition from semiconductor to near-metallic at these pressures which are in the range 3.0-5.0 GPa. This transition pressure is seen to decrease with the increase in the percentage content of thallium due to increasing metallicity of the thallium. The transition is reversible under application of pressure and X-ray diffraction of samples recovered after pressurization show that they remain amorphous after undergoing a pressurization decompression cycle.

Variation of Electrical Resistivity with High Pressure in Ge-Te-Sn Glasses: A Composition Dependent Study

The variation of normalized electrical resistivity in the system of glasses Ge15Te85-xSnx with (1 <= x <= 5) has been studied as a function of high pressure for pressures up to 9.5 GPa. It is found that with the increase in pressure, the resistivity decreases initially and shows an abrupt fall at a particular pressure, indicating the phase transition from semiconductor to near metallic at these pressures, which lie in the range 1.5-2.5 GPa, and then continues being metallic up to 9.5 GPa. This transition pressure is seen to decrease with the increase in the percentage content of tin due to increasing metallicity of tin. The semiconductor to near metallic transition is exactly reversible and may have its origin in a reduction of the band gap due to high pressure.

Stabilization of the high-temperature and high-pressure cubic phase of ZnO by temperature-controlled milling

The reversible transition of wurtzite to rock salt phase under pressure is well reported in literature. The cubic phase is unstable under ambient conditions both in the bulk and in nanoparticles. This paper reports defect-induced stabilization of cubic ZnO phase in sub 20 nm ZnO particles and explores their optical properties. The size reduction was achieved by ball milling in a specially designed mill which allows a control of the milling temperature. The process of synthesis involved both variation of milling temperature (including low temperature similar to 150 K) and impact pressure. We show that these have profound influence in the introduction of defects and stabilization of the cubic phase. A molecular dynamics simulation is presented to explain the observed results. The measured optical properties have further supported the observations of defect-induced stabilization of cubic ZnO and reduction in particle size.

Neoarchean arc magmatism followed by high-temperature, high-pressure metamorphism in the Nilgiri Block, southern India

The Nilgiri Block, southern India is an exhumed lower crust formed through arc magmatic processes in the Neoarchean. The main lithologies in this terrane include charnockites, gneisses, volcanic tuff, metasediments, banded iron formation and mafic-ultramafic bodies. Mafic-ultramafic rocks are present towards the northern and central part of the Nilgiri Block. We examine the evolution of these mafic granulites/metagabbros by phase diagram modeling and U-Pb sensitive high resolution ion microprobe (SHRIMP) dating. They consist of a garnet-clinopyroxene-plagioclase-hornblende-ilmenite +/- orthopyroxene +/- rutile assemblage. Garnet and clinopyroxene form major constituents with labradorite and orthopyroxene as the main mineral inclusions. Labradorite, identified using Raman analysis, shows typical peaks at 508 cm(-1), 479 cm(-1), 287 cm(-1) and 177 cm(-1). It is stable along with orthopyroxene towards the low-pressure high-temperature region of the granulite fades (M1 stage). Subsequently, orthopyroxene reacted with plagioclase to form the peak garnet + clinopyroxene + rutile assemblage (M2 stage). The final stage is represented by amphibolite facies-hornblende and plagioclase-rim around the garnet-clinopyroxene assemblage (M3 stage). Phase diagram modeling shows that these mafic granulites followed an anticlockwise P-T-t path during their evolution. The initial high-temperature metamorphism (M1 stage) was at 850-900 degrees C and similar to 9 kbar followed by high-pressure granulite fades metamorphism (M2 stage) at 850-900 degrees C and 14-15 kbar. U-Pb isotope studies of zircons using SHRIMP revealed late Neoarchean to early paleoproterozoic ages of crystallization and metamorphism respectively. The age data shows that these mafic granulites have undergone arc magmatism at ca. 25392 +/- 3 Ma and high-temperature, high-pressure metamorphism at ca. 2458.9 +/- 8.6 Ma. Thus our results suggests a late Neoarchean arc magmatism followed by early paleoproterozoic high-temperature, high-pressure granulite facies metamorphism due to the crustal thickening and suturing of the Nilgiri Block onto the Dharwar Craton. (C) 2015 Elsevier B.V. All rights reserved.

Evolution of high-pressure mafic granulites and pelitic gneisses from NE Madagascar: Tectonic implications

The occurrence of high-pressure mafic-ultramafic bodies within major shear zones is one of the indicators of paleo-subduction. In mafic granulites of the Andriamena complex (north-eastern Madagascar) we document unusual textures including garnet-clinopyroxene-quartz coronas that formed after the breakdown of orthopyroxene-plagioclase-ilmenite. Textural evidence and isochemical phase diagram calculations in the Na2O-CaO-K2O-FeO-MgO-Al2O3-SiO2-H2O-TiO2 system indicate a pressure-temperature (P-T) evolution from an isothermal (780 degrees C) pressure up to c. 24 kbar to decompression and cooling. Such a P-T trajectory is typically attained in a subduction zone setting where a gabbroic/ultramafic complex is subducted and later exhumed to the present crustal level during oceanic closure and final continental collision. The present results suggest that the presence of such deeply subducted rocks of the Andriamena complex is related to formation of the Betsimisaraka suture. LA-ICPMS U-Pb zircon dating of pelitic gneisses from the Betsimisaraka suture yields low Th/U ratios and protolith ages ranging from 2535 to 2625 Ma. A granitic gneiss from the Alaotra complex yields a zircon crystallization age of ca. 818 Ma and Th/U ratios vary from 1.08 to 2.09. K-Ar dating of muscovite and biotite from biotite-kyanite-sillimanite gneiss and garnet-biotite gneiss yields age of 486 +/- 9 Ma and 459 +/- 9 Ma respectively. We have estimated regional crustal thicknesses in NE Madagascar using a flexural inversion technique, which indicates the presence of an anomalously thick crust (c. 43 km) beneath the Antananarivo block. This result is consistent with the present concept that subduction beneath the Antananarivo block resulted in a more competent and thicker crust. The textural data, thermodynamic model, and geophysical evidence together provide a new insight to the subduction history, crustal thickening and evolution of the high-pressure Andriamena complex and its link to the terminal formation of the Betsimisaraka suture in north-eastern Madagascar. (C) 2015 Elsevier B.V. All rights reserved.

Effect Of High Pressure On The Electrical Resistivity Of Ge-Te In Glasses

The variation in the electrical resistivity of the chalcogenide glasses Ge15Te85-x has been studied as a function of high pressure for pressures up to 8.5GPa. All the samples studied undergo a semi-conductor to metallic transition in a continuous manner at pressures between 1.5-2.5GPa. The transition pressure at which the samples turn metallic increases with increase in percentage of Indium. This increase is a direct consequence of the increase in network rigidity with the addition of Indium. At a constant pressure of 0.5GPa, the normalized resistivity shows some signature of the existence of the intermediate phase. Samples recovered after a pressure cycle remain amorphous suggesting that the semi-conductor to metallic transition arises from a reduction of the band gap due to pressure or the movement of the Fermi level into the conduction or valence band.