Effect of pressure on the electrical resistivity of bulk Ge20Te80 glass

An irreversible pressure induced semiconductor-to-metal transition in bulk Ge20Te80 glass is observed at about 5 GPa pressure. The high pressure phase has a face centered cubic structure with a lattice constant 6.42 A° as deduced by X-ray diffraction studies on the pressure quenched samples. The temperature and pressure dependence of the electrical resistivity confirms the observed transition to be a semiconductor-to-metal transition. The temperature dependence of thermo electric power is also reported.

Purification and Regulatory Properties of Mung Bean (Vigna Radiata L.) Serine Hydroxymethyltransferase 1

Serine hydroxymethyltransferase, the first enzyme in the pathway for interconversion of C1 fragments, was purified to homogeneity for the first time from any plant source. The enzyme from 72-h mung bean (Vigna radiata L.) seedlings was isolated using Blue Sepharose CL-6B and folate-AH-Sepharose-4B affinity matrices and had the highest specific activity (1.33 micromoles of HCHO formed per minute per milligram protein) reported hitherto. The enzyme preparation was extremely stable in the presence of folate or L-serine. Pyridoxal 5'-phosphate, ethylenediaminetetraacetate and 2-mercaptoethanol prevented the inactivation of the enzyme during purification. The enzyme functioned optimally at pH 8.5 and had two temperature maxima at 35 and 55°C. The Km values for serine were 1.25 and 68 millimolar, corresponding to Vmax values of 1.8 and 5.4 micromoles of HCHO formed per minute per milligram protein, respectively. The K0.5 value for L-tetrahydrofolate (H4folate) was 0.98 millimolar. Glycine, the product of the reaction and D-cycloserine, a structural analog of D-alanine, were linear competitive inhibitors with respect to L-serine with Ki values of 2.30 and 2.02 millimolar, respectively. Dichloromethotrexate, a substrate analog of H4folate was a competitive inhibitor when H4folate was the varied substrate. Results presented in this paper suggested that pyridoxal 5'-phosphate may not be essential for catalysis.The sigmoid saturation pattern of H4folate (nH = 2.0), one of the substrates, the abolition of sigmoidicity by NADH, an allosteric positive effector (nH = 1.0) and the increase in sigmoidicity by NAD+ and adenine nucleotides, negative allosteric effectors (nH = 2.4) clearly established that this key enzyme in the folate metabolism was an allosteric protein. Further support for this conclusion were the observations that (a) serine saturation exhibited an intermediary plateau region; (b) partial inhibition by methotrexate, aminopterin, O-phosphoserine, DL-{alpha}-methylserine and DL-O-methylserine; (c) subunit nature of the enzyme; and (d) decrease in the nH value from 2.0 for H4folate to 1.5 in presence of L-serine. These results highlight the regulatory nature of mung bean serine hydroxymethyltransferase and its possible involvement in the modulation of the interconversion of folate coenzymes.

The Crystal and Molecular Structure of 4-Aza-5-oxo-tricyclo[4.4.0.03,8]decane (Aza-twistanone)

Die kristalline Struktur von Aza-twistanon wurde durch eine Röntgenstruktur-analyse untersucht. Die Kristalle gehören zur monoklinen Raumgruppe P21/n mit den Zelldimensionen a = 6,662(6), b = 13,36(2), c = 8,606(9) Å, = 98,97(2)°, V = 757 Å3, Z = 4. Die Struktur wurde mit Direktmethoden gelöst und bis zu R = 0,035 verfeinert (mittlere (c) = 0,003 Å3).Die cis-Amidgruppe ist relativ stark deformiert und hat einen Torsionswinkel C -C -N-C von 14,5(4)° (Deformation aus der Ebene c = 5,0(5)° und N = 13,5(4,0)°). Die gegenüberliegende äthylenbrücke weist einen Torsionswinkel von 25,1(5)° auf. Die entsprechenden Winkel in Twistan betragen je 20°. Das tricyclische Gerüst von Aza-twistanon hat approximative.

Triassic eclogite from northern Vietnam: inferences and geological significance

The first finding of low-temperature eclogites from the Indochina region is reported. The eclogites occur along the Song Ma Suture zone in northern Vietnam, which is widely regarded as the boundary between the South China and Indochina cratons. The major lithology of the area is pelitic schist that contains garnet and phengite with or without biotite, chloritoid, staurolite and kyanite, and which encloses blocks and lenses of eclogite and amphibolite. The eclogites commonly consist of garnet, omphacite, phengite, rutile, quartz and/or epidote with secondary barroisite. Omphacite is commonly surrounded by a symplectite of Na-poor omphacite and Na-rich plagioclase. In highly retrograded domains, diopside + tremolite + plagioclase symplectites replace the primary phases. Estimated peak-pressure metamorphic conditions based on isochemical phase diagrams for the eclogites are 2.1-2.2 GPa and 600-620 degrees C, even though thermobarometric results yield higher pressure and temperature conditions (2.6-2.8 GPa and 620-680 degrees C). The eclogites underwent a clockwise P-T trajectory with a post-peak-pressure increase of temperature to a maximum of > 750 degrees C at 1.7 GPa and a subsequent cooling during decompression to 650 degrees C and 1.3 GPa, which was followed by additional cooling before close-to-isothermal decompression to similar to 530 degrees C at 0.5 GPa. The surrounding pelitic schist (garnet-chloritoid-phengite) records similar metamorphic conditions (580-600 degrees C at 1.9-2.3 GPa) and a monazite chemical age of 243 +/- 4 Ma. A few monazite inclusions within garnet and the cores of some zoned monazite in garnet-phengite schist record an older thermal event (424 +/- 15 Ma). The present results indicate that the Indochina craton was deeply (> 70 km) subducted beneath the South China craton in the Triassic. The Silurian cores of monazite grains may relate to an older non-collisional event in the Indochina craton.

Isomerisation of 1-methylene-2-methyl-2-(2-oxopropyl)-cyclohexanes to 2-methylene-1-methyl-1-(2-oxopropyl)-cyclohexanes by ene and retro-ene reaction

Thermal activation of the normal Claisen products, the enones 4 7 and 14 in the presence of a catalytic amount of propionic acid generated the isomeric enones 6 9 and 15 via the sequential intramolecular ene-reaction of the enol tautomer followed by 1,5-hydrogen transfer (or retro ene-reaction) of the resultant acetyl cyclopropane intermediate. conversion of the enones 9 and 15 into the corresponding cyclohexenones 10 and 16 established the structures of the rearrangement products.

Substrate-dependent structure, microstructure, composition and properties of nanostructured TiN films

Titanium nitride films of a thickness of similar to 1.5 mu m were deposited on amorphous and crystalline substrates by DC reactive magnetron sputtering at ambient temperature with 100% nitrogen in the sputter gas. The growth of nanostructured, i.e. crystalline nano-grain sized, films at ambient temperature is demonstrated. The microstructure of the films grown on crystalline substrates reveals a larger grain size/crystallite size than that of the films deposited on amorphous substrates. Specular reflectance measurements on films deposited on different substrates indicate that the position of the Ti-N 2s band at 2.33 eV is substrate-dependent, indicating substrate-mediated stoichiometry. This clearly demonstrates that not only structure and microstructure, but also chemical composition of the films is substrate-influenced. The films deposited on amorphous substrates display lower hardness and modulus values than the films deposited on crystalline substrates, with the highest value of hardness being 19 GPa on a lanthanum aluminate substrate. (C) 2011 Elsevier Ltd. All rights reserved.

Magnetic properties of rare earth nickelates of the Ln(2)BaNiO(5) family

Rare-earth nickelates Ln(2)BaNi(1-x)Cu(2)O(5), Ln = Nd and Dy, and Dy2-xYxBaNiO5 have been synthesized in order to investigate the effect of substitution of Ni by Cu and Dy by nonmagnetic Y on the magnetic properties of the nickelates. In Ln(2)BaNi(1-x)Cu(x)O(5), the nickelate structure (x=0.0) changes to the cuprate structure (x=1.0) at a specific composition (x=0.3). The Neel temperature of Nd2BaNi1-xCuxO5 decreases continuously with increase in x upto x=0.3 (T-N = 18K); when x > 0.3, the materials are paramagnetic down to 20K. The mu(eff) in Nd2BaNi1-xCxO5 essentially corresponds to the contribution of the Nd ions. In Dy2-xYxBaNiO5, the Neel temperature decreases from 40K when x=0.0 to 24K when x=1.5. The compositions with 1.5 less than or equal to x less than or equal to 2 (including the x=1.95 composition) are paramagnetic down to 20K, unlike Y2BaNiO5 (x=2.0) which exhibits a T-N of 370K. Even the smallest concentration of paramagnetic Dy seems to destroy the antiferromagnetic Ni-O-Ni chains in Y2BaNiO5.

Phonon interference in BaTiO3: High-pressure Raman study

Raman experiments have been carried out on single crystals of BaTiO3 as a function of pressure up to 3.5 GPa across the ferroelectric (tetragonal) to paraelectric (cubic) phase transition. The unusual features in the Raman spectra associated with the interference effects due to coupling of the three A1(TO) phonons are studied quantitatively to obtain the pressure dependence of the line shape parameters and the coupling constants. The frequencies of the middle and highest-frequency modes as well as the linewidth of the middle mode show interesting pressure dependence.

ChemInform Abstract: Synthesis Based on Cyclohexadienes. Part 16. Synthesis of Methyl 2,7-Dimethyltricyclo (5.2.2.01,5)undec-5-ene-6-carboxylates

Synthesis of methyl 2, 7-dimethyltricyclo{5.2.2.0(1,5}undec-5-en-6-carboxylates, the tricyclic skeleton present in (+)-allo-cedrol (1) is described using the Diels-Alder strategy. Thus, Birch reduction of the aromatic acid 8 gives 5, the methyl ester of which is isomerised with DBU to a 1:1 mixture of the dienes 6 and 4. Cycloaddition of this mixture with 2-chloroacrylonitrile followed by hydrolysis yields the ketone 60 having the tricyclo{5.2.2.0(1.5)}undec-5-ene framework. Similar reaction with methyl vinyl ketone affords the regioisomeric adducts 61 and 62.

Synthetic studies towards novel terpenic natural products kelsoene and poduran: Construction of the complete 4-5-5-fused tricarbocyclic core

A common synthetic approach to the recently reported sesquiterpene kelsoene 1 and the tetraterpene poduran 5, bearing a novel tricyclo[6.2.0.0(2,6)]decane framework, from commercially available 1,5-COD and leading to the first construction of the carbocyclic core present in these natural products is delineated.

Electrochemical tuning and mechanical resilience of single-wall carbon nanotubes

Single-wall carbon nanotubes (SWNTs) are fascinating systems exhibiting many novel physical properties. In this paper, we give a brief review of the structural, electronic, vibrational, and mechanical properties of carbon nanotubes. In situ resonance Raman scattering of SWNTs investigated under electrochemical biasing demonstrates that the intensity of the radial breathing mode varies significantly in a nonmonotonic manner as a function of the cathodic bias voltage, but does not change appreciably under anodic bias. These results can be quantitatively understood in terms of the changes in the energy gaps between the 1 D van Hove singularities in the electron density of states, arising possibly due to the alterations in the overlap integral of pi bonds between the p-orbitals of the adjacent carbon atoms. In the second part of this paper, we review our high-pressure X-ray diffraction results, which show that the triangular lattice of the carbon nanotube bundles continues to persist up to similar to10 GPa. The lattice is seen to relax just before the phase transformation, which is observed at similar to10 GPa. Further, our results display the reversibility of the 2D lattice symmetry even after compression up to 13 GPa well beyond the 5 GPa value observed recently. These experimental results explicitly validate the predicted remarkable mechanical resilience of the nanotubes.

Pressure-induced phase transitions in alpha-ZrMo2O8

We report high-pressure Raman, infrared (IR), and optical-absorption spectra of alpha-ZrMo2O8 (trigonal) up to 38 GPa at room temperature. The spectroscopic studies are consistent with diffraction results that show that alpha-ZrMo2O8 transforms into delta-ZrMo2O8 (monoclinic) at about 1 GPa and the delta phase converts to the epsilon phase (trielinic) at about 2.0 GPa. Optical-absorption measurements give an estimate of the band gap of about 0.6 eV at the lowest pressure. Band-gap changes with pressure are confirmed with visual observations. ZrMo2O8 changes from transparent at 5 GPa to yellow at 10 GPa, red at 18 GPa, and at about 30 GPa it becomes opaque.

Structural changes in single-walled carbon nanotubes under non-hydrostatic pressures: x-ray and Raman studies

Using in situ x-ray diffraction and Raman scattering techniques, we have investigated the behaviour of single-walled carbon nanotubes bundles under non-hydrostatic pressures. It is seen that the diffraction line corresponding to the two-dimensional triangular lattice in the bundles is not reversible for pressures beyond 5 GPa, in sharp contrast to earlier results under hydrostatic pressure conditions. Most interestingly, radial breathing and tangential Raman modes of the pressure-cycled samples from 21 and 30 GPa match very well with those of the starting sample. Raman and x-ray results put together clearly suggest that the ordering of tubes in the bundles is only marginally regained with a very short coherence length on decompression.

Synthesis based on cyclohexadienes Part 36: an efficient methodology for the construction of spiro[4.5]decanes: a formal synthesis of acorone

An efficient strategy for the contruction of spiro[4.5] decanes is described and involves a bridgehead substitution of a methoxyl group by a methyl group followed by an oxidative cleavage of the tricyclo[5.2.2.0(1,5)] undecane 25 to produce the spiro[4.5] decanes 31 & 32 which are intermediates in the synthesis of acorone. A novel one-pot conversion of alpha-methoxy carboxylic acid to alpha-methyl carboxylic acid is described.

Evolution of 1/f α noise during electromigration stressing of metal film: Spectral signature of electromigration process

In this paper we report a systematic study of low-frequency 1/fα resistance fluctuation in a metal film at different stages of electromigration. The resistance fluctuation (noise) measurement was carried out in presence of a dc electromigration stressing current. We observe that in addition to the increase in the spectral power SV(f), the frequency dependence of the spectral power changes as the electromigration process progresses and the exponent α starts to change from 1 to higher value closer to 1.5. We interpret this change in α as arising due to an additional contribution to the spectral power with a 1/f3/2 component, which starts to contribute as the electromigration process progresses. This additional component SV(f) ∼ 1/f3/2 has been suggested to originate from long range diffusion that would accompany any electromigration process. The experimental observation finds support in a model simulation, where we also find that the enhancement of noise during electromigration stressing is accompanied by a change in spectral power frequency dependence.