Counterclockwise exhumation of a hot orogen: The Paleoproterozoic ultrahigh-temperature granulites in the North China Craton

Regional metamorphic belts provide important constraints on the plate tectonic architecture of orogens. We report here a detailed petrologic examination of the sapphirine-bearing ultra-high temperature (UHT) granulites from the Jining Complex within the Khondalite Belt of the North China Craton (NCC). These granulites carry diagnostic UHT assemblages and their microstructures provide robust evidence to trace the prograde, peak and retrograde metamorphic evolution. The P–T conditions of the granulites estimated from XMgGrt(Mg/Fe + Mg) − XMgSpr isopleth calculations indicate temperature above 970 °C and pressures close to 7 kbar. We present phase diagrams based on thermodynamic computations to evaluate the mineral assemblages and microstructures and trace the metamorphic trajectory of the rocks. The evolution from Spl–Qtz–Ilm–Crd–Grt–Sil to Spr–Qtz–Crd–Opx–Ilm marks the prograde stage. The Spl–Qtz assemblage appears on the low-pressure side of the P–T space with Spr–Qtz stable at the high-pressure side, possibly representing an increase in pressure corresponding to compression. The spectacular development of sapphirine rims around spinel enclosed in quartz supports this inference. An evaluation of the key UHT assemblages based on model proportion calculation suggests a counterclockwise P–T path. With few exceptions, granulite-facies rocks developed along collisional metamorphic zones have generally been characterized by clockwise exhumation trajectories. Recent evaluation of the P–T paths of metamorphic rocks developed within collisional orogens indicates that in many cases the exhumation trajectories follow the model subduction geotherm, in accordance with a tectonic model in which the metamorphic rocks are subducted and exhumed along a plate boundary. The timing of UHT metamorphism in the NCC (c. 1.92 Ga) coincides with the assembly of the NCC within the Paleoproterozoic Columbia supercontinent, a process that would have involved subduction of passive margins sediments and closure of the intervening ocean. Thus, the counterclockwise P–T path obtained in this study correlates well with a tectonic model involving subduction and final collisional suturing, with the UHT granulites representing the core of the hot or ultra-hot orogen developed during Columbia amalgamation.

Biosynthesis of coenzyme Q in microorganisms

Incorporation of mevalonate-2-C14, acetate-1-C14, and formate-C14 into the lipids of microorganisms was studied. In the case of four bacteria tested—Agrobacterium tumefaciens, Azotobacter vinelandii, Escherichia coli, and a Pseudomonas species—the various homologues of coenzyme Q present were not labeled with any of the tracers used, although significant amounts of radioactivity were present in the lipids. Both acetate and mevalonate were incorporated into coenzyme Q and sterol of the moulds, Aspergillus niger, Neurospora crassa, Penicillium chrysogenum, and Gibberella fujickuroi, and a yeast, Torulopsis utilis. Mevalonate was incorporated into the side chain but not the ring, whereas acetate was incorporated into both. It appears that the mevalonate pathway for the synthesis of coenzyme Q is operative only in those organisms which also contain other isoprene compounds such as sterol and carotene.

Competing magnetic interactions in a dinuclear Ni(II) complex: Antiferromagnetic O-H center dot center dot center dot O moiety and ferromagnetic N-3(-) ligand

Synthesis, structural characteristics, magnetic studies and DFT calculations in Ni(II) dinuclear complexes containing two bridging N-3(-) and an O-(HO)-O-... linkage reveal the existence of ferromagnetic interactions between Ni(II) centers via N-3(-) ligands and antiferromagnetic interactions through the H-bonded moiety. The overall magnetic behavior of the system depends on the delicate balance between these two competing interactions.

New transparent crystallized glasses with optical nonlinear LiBGeO4 crystals

Crystallization behaviors of the glass with a composition of 25Li(2)O.25B(2)O(3).50GeO(2) corresponding to lithium borogermanate LiBGeO4 have been examined. It has been confirmed that the LiBGeO4 crystalline phase is formed at the surface of heat-treated glasses. The second harmonic (SH) generation is found from transparent surface crystallized glasses, demonstrating for the first time that the LiBGeO4 phase shows optical nonlinearity. The SH intensity of LiBGeO4 crystallites (powdered state) prepared through crystallization is about ten times as large as that of pulverized alpha-quartz. The SH intensity of transparent crystallized glasses (bulk state) with crystalline layers of 3-4.5 mum thickness increases with increasing heat treatment temperature (540-560degreesC) and time (1-6 h), and the maximum SH intensity among the samples studied is in the order of 1/10 in comparison with that of alpha-quartz single crystal. The transparent crystallized glass obtained by heat treatment at 550alphaC for 3 h exhibits a clear and fine Maker fringe pattern, indicating a highly orientation of LiBGeO4 crystals at the surface.

High contrast imaging and thickness determination of graphene with in-column secondary electron microscopy

We report a new method for quantitative estimation of graphene layer thicknesses using high contrast imaging of graphene films on insulating substrates with a scanning electron microscope. By detecting the attenuation of secondary electrons emitted from the substrate with an in-column low-energy electron detector, we have achieved very high thickness-dependent contrast that allows quantitative estimation of thickness up to several graphene layers. The nanometer scale spatial resolution of the electron micrographs also allows a simple structural characterization scheme for graphene, which has been applied to identify faults, wrinkles, voids, and patches of multilayer growth in large-area chemical vapor deposited graphene. We have discussed the factors, such as differential surface charging and electron beam induced current, that affect the contrast of graphene images in detail. (C) 2011 American Institute of Physics. doi:10.1063/1.3608062]

Simulation of Influence of Bilayer Melting on Dynamics and Thermodynamics of Interfacial Water

We investigate the effect of bilayer melting transition on thermodynamics and dynamics of interfacial water using molecular dynamics simulation with the two-phase thermodynamic model. We show that the diffusivity of interface water depicts a dynamic crossover at the chain melting transition following an Arrhenius behavior until the transition temperature. The corresponding change in the diffusion coefficient from the bulk to the interface water is comparable with experimental observations found recently for water near 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) vesicles Phys. Chem. Chem. Phys. 13, 7732 (2011)]. The entropy and potential energy of interfacial water show distinct changes at the bilayer melting transition, indicating a strong correlation in the thermodynamic state of water and the accompanying first-order phase transition of the bilayer membrane. DOI: 10.1103/PhysRevLett.110.018303

The effect of alloy composition on instabilities in the beta phase of titanium alloys

A metastable nano-scale disordered precipitate with orthorhombic symmetry has been identified using high resolution scanning transmission electron microscopy. The phase, termed O', is metastable, formed by a shuffle mechanism involving a {110}<1<(1)over bar>0> transverse phonon wave in samples of Ti-26Nb-2Zr (at.%) quenched from the beta phase. The addition of 2% Zr to Ti-26Nb appears to suppress significantly the stability of both the {11 (2) over bar}<111> shear and 2/3 <111> longitudinal phonon wave but promotes the {110}<1<(1)over bar>0> transverse shuffle. This results in the nano-size O' phase being homogeneously formed in the parent beta phase matrix rather than the massive alpha `' phase. (C) 2016 Elsevier B.V. All rights reserved.

A nano-scale instability in the beta phase of dilute Ti-Mo alloys

A nano-scale instability in the beta phase resulting in the formation of the disordered orthorhombic O' phase has been discovered in a fairly dilute binary Ti-Mo alloy, using selected area electron diffraction and high resolution scanning transmission electron microscopy. The O' phase informed in the alloy when the Mo content exceeds a critical value. The instability occurs in beta-solutionized samples that have been quenched to room temperature and is found to co-exist with athermal omega to phase. Interestingly, this nano-scale instability, involving the {110}<1<(1)over bar>0> soft-phonon shuffle, occurs in the beta phase without deliberate additions of either interstitial or substitutional solutes. (C) 2016 Elsevier Ltd. All rights reserved.

Hydroxylation of oxygen-covered Cu(110) and Zn(0001) surfaces by interaction with CH3OH, (CH3)2NH, H2S, HCl and other proton donor molecules

EELS studies provide definitive evidence for the hydroxylation of oxygen-covered Cu(110) and Zn(0001) surfaces on interaction with proton donor molecules such as H2O, CH3OH, HCOOH, NH3 and (CH3)2NH. The occurrence of surface hydroxylation is unambigouusly shown by a study of the interaction of H2S and HCl with an oxygen covered Cu(110) surface.

Biosynthesis of isoleucine and valine in mycobacterium tuberculosis H37Rv*1: II. Purification and properties of acetohydroxy acid isomerase

Acetohydroxy acid isomerase (AHA isomerase) was purified about 110-fold and separated from reductase and acetohydroxy acid isomeroreductase. The AHA isomerase was found to be homogeneous by agar and polyacrylamide gel electrophoreses at different pHs. The properties of AHA isomerase have been studied. The purified enzyme showed requirement for Image -ascorbic acid and sulfate ions for its activity. Synthetic ascorbic acid sulfate could replace Image -ascorbic acid and sulfate. α-Methyllactate and α-ketoisovalerate were found to inhibit AHA isomerase activity competitively whereas Image -valine and Image -isoleucine had no significant inhibitory effect. p-Hydroxymercuribenzoate inhibited AHA isomerase activity and the inhibition was reversed by β-mercaptoethanol.

Effect of HCl on the adsorption of oxygen on Cu(110) surface: An eels study

Oxygen is shown to adsorb molecularly on a clean Cu(110) surface at 80 K and dissociate around 150 K forming atomic oxygen. Adsorption of oxygen on an HCl covered surface at low temperatures results in the formation of adsorbed hydroxyl groups and water in addition to adsorbed molecular oxygen. The molecular oxygen species is stable up to 190 K on the HCl covered surface.

Coherent phonons in pyrochlore titanates A(2)Ti(2)O(7) (A = Dy, Gd, Tb): A phase transition in Dy2Ti2O7 at 110 K

We study the generation of coherent optical phonons in spin-frustrated pyrochlore single crystals Dy2Ti2O7, Gd2Ti2O7, and Tb2Ti2O7 using femtosecond laser pulses (65 fs, 1.57 eV) in degenerate time-resolved transmission experiments as a function of temperature from 4 to 296 K. At 4 K, two coherent phonons are observed at similar to 5.3 THz (5.0 THz) and similar to 9.3 THz (9.4 THz) for Dy2Ti2O7 (Gd2Ti2O7), whereas three coherent phonons are generated at similar to 5.0, 8.6, and 9.7 THz for Tb2Ti2O7. In the case of spin-ice Dy2Ti2O7, a clear discontinuity is observed in the linewidths of both the coherent phonons as well as in the phase of lower-energy coherent phonon mode, indicating a subtle structural change at 110 K. Another important observation is a phase difference of pi between the modes in all the samples, thus suggesting that the driving forces behind the generation of these modes could be different in nature, unlike a purely impulsive or displacive mechanism.

Coadsorption of Dioxygen and Water on the Ni(110) Surface: Role of O1--Type Species in the Dissociation of Water

While the adsorption of dioxygen at a clean Ni(110) surface gives rise to two O(1s) features at 531 and 530 eV assigned to O-(a) and O2-(a) type species respectively, coadsorption of dioxygen and water mixtures result in the additional formation of hydroxyl species characterized by an O(1s) peak at 532.3 eV. The latter is attributed to the oxygen induced dissociation of water via a low energy pathway involving the O-(a)-type species. The proportions of the O-(a) and the hydroxyl species are greater for small O-2/H2O ratios and lower temperatures (120 K). With increase in temperature, the relative surface concentrations of the O-(a) and the hydroxyl species decrease while there is an increase in the concentration of the oxidic O2-(a) species. Thus, the surface concentrations of both the hydroxyl and the O2-(a) species depend critically on the presence of O- type species. Above 300K the surface chemistry in the main involves the conversion of O- to O2- species via the hydroxyl species.

Nature of the Oxygen Species at Ni(110) and Ni(100) Surfaces Revealed by Exposure to Oxygen and Oxygen-Ammonia Mixtures: Evidence for the Surface Reactivity of O- Type Species

Adsorption of dioxygen at clean Ni(110) and Ni(100) surfaces gives rise to two prominent features in the O(1s) spectra at 530 and 531 eV due to O2- and O- type species, respectively. Interaction of ammonia with a Ni(100)-O surface where theta(oxygen) < 0.1 ML favors the dissociation of NH3 giving NHn, (n = 1, 2) and N(a) species. This is accompanied by a decrease in the intensity of the 531 eV feature. On the other hand. a Ni(100)-O surface where the oxygen species are mainly of the O2- type is unreactive, Coadsorption studies of NH3-O-2 mixtures show that at Ni(110) surfaces the uptake of both oxygen and ammonia increase with the proportion of oxygen in the NH3-O-2 mixture. The surface concentrations of the O- species and the NHn species also increase with the increase in the O-2/NH3 ratio while the slope of the plot of sigma(N) versus sigma(O-) is around unity. The results demonstrate the high surface reactivity of the O- species and its role in the dissociation of ammonia. Based on these observations, the possibility of the formation of a surface complex between ammonia and oxygen (specifically O-) is suggested. Results from vibrational spectroscopic studies of the coadsorption of NH3-O-2 mixtures are consistent with those from core-level spectroscopic studies.

Dielectric properties of (110) oriented PbZrO3 and La-modified PbZrO3 thin films grown by sol-gel process on Pt(111)/Ti/SiO2/Si substrate

Highly (110) preferred orientated antiferroelectric PbZrO3 (PZ) and La-modified PZ thin films have been fabricated on Pt/Ti/SiO2/Si substrates using sol-gel process. Dielectric properties, electric field induced ferroelectric polarization, and the temperature dependence of the dielectric response have been explored as a function of composition. The Tc has been observed to decrease by ∼ 17 °C per 1 mol % of La doping. Double hysteresis loops were seen with zero remnant polarization and with coercive fields in between 176 and 193 kV/cm at 80 °C for antiferroelectric to ferroelectric phase transformation. These slim loops have been explained by the high orientation of the films along the polar direction of the antiparallel dipoles of a tetragonal primitive cell and by the strong electrostatic interaction between La ions and oxygen ions in an ABO3 perovskite unit cell. High quality films exhibited very low loss factor less than 0.015 at room temperature and pure PZ; 1 and 2 mol % La doped PZs have shown the room temperature dielectric constant of 135, 219, and 142 at the frequency of 10 kHz. The passive layer effects in these films have been explained by Curie constants and Curie temperatures. The ac conductivity and the corresponding Arrhenius plots have been shown and explained in terms of doping effect and electrode resistance.