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1.
Rev Sci Instrum ; 79(8): 085103, 2008 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-19044376

RESUMO

In this paper we describe a prototype of a diamond anvil cell (DAC) for high pressure/high temperature studies. This DAC combines the use of a resistive oven of 250 W power in a very small volume, associated with special conical seats for Boehler-type diamond anvils in order to have a large angular acceptance. To protect the diamond anvils from burning and to avoid the oven oxidation, the heated DAC is enclosed in a vacuum chamber. The assemblage was used to study the melting curve of germanium at high pressure (up to 20 GPa) and high temperature (up to 1200 K) using x-ray diffraction and x-ray absorption spectroscopy.


Assuntos
Absorciometria de Fóton , Pressão Atmosférica , Diamante/química , Calefação , Difração de Raios X , Desenho de Equipamento , Germânio/química , Teste de Materiais/métodos , Fenômenos Físicos , Termodinâmica
2.
J Phys Chem B ; 112(4): 1095-103, 2008 Jan 31.
Artigo em Inglês | MEDLINE | ID: mdl-18181605

RESUMO

Angle dispersion X-ray diffraction (AXDX) experiments on nitromethane single crystals and powder were performed at room temperature as a function of pressure up to 19.0 and 27.3 GPa, respectively, in a membrane diamond anvil cell (MDAC). The atomic positions were refined at 1.1, 3.2, 7.6, 11.0, and 15.0 GPa using the single-crystal data, while the equation of state (EOS) was extended up to 27.3 GPa, which is close to the nitromethane decomposition threshold pressure at room temperature in static conditions. The crystal structure was found to be orthorhombic, space group P2(1)2(1)2(1), with four molecules per unit cell, up to the highest pressure. In contrast, the molecular geometry undergoes an important change consisting of a gradual blocking of the methyl group libration about the C-N bond axis, starting just above the melting pressure and completed only between 7.6 and 11.0 GPa. Above this pressure, the orientation of the methyl group is quasi-eclipsed with respect to the NO bonds. This conformation allows the buildup of networks of strong intermolecular O...H-C interactions mainly in the bc and ac planes, stabilizing the crystal structure. This structural evolution determines important modifications in the IR and Raman spectra, occurring around 10 GPa. Present measurements of the Raman and IR vibrational spectra as a function of pressure at different temperatures evidence the existence of a kinetic barrier for this internal rearrangement.

3.
Phys Rev Lett ; 93(9): 095502, 2004 Aug 27.
Artigo em Inglês | MEDLINE | ID: mdl-15447111

RESUMO

We have measured the isothermal equation of state (EOS) of osmium to 75 GPa under hydrostatic conditions at room temperature using angle-dispersive x-ray diffraction. A least-squares fit of this data using a third-order Birch-Murnaghan EOS yields an isothermal bulk modulus K0=411+/-6 GPa, showing osmium is more compressible than diamond. Most importantly, we have documented an anomaly in the compressibility around 25 GPa associated with a discontinuity in the first pressure derivative of the c/a ratio. This discontinuity plausibly arises from the collapse of the small hole-ellipsoid in the Fermi surface near the L point.

4.
Biochem Biophys Res Commun ; 312(1): 197-203, 2003 Dec 05.
Artigo em Inglês | MEDLINE | ID: mdl-14630042

RESUMO

The effect of the hydrostatic pressure on the CO ligand stretch vibration in cytochrome P450cam-CO bound with various substrates is studied by FTIR. The vibration frequency is linearily shifted to lower values with increasing pressure. The slope of the shift gives the isothermal compressibility of the heme pocket and is found to be related to the high-spin state content in an opposite direction to that previously observed from the pressure-induced shift of the Soret band. This opposite behaviour is explained by the dual effect of heme pocket water molecules both on the CO ligand and on electrostatic potentials produced by the protein at the distal side. The latter effect disturbs ligand-distal side contacts which are needed for a specific proton transfer in oxygen activation when dioxygen is the ligand. Their loss results in uncoupled H(2)O(2) formation.


Assuntos
Cânfora 5-Mono-Oxigenase/química , Monóxido de Carbono/química , Heme/química , Pressão Hidrostática , Espectroscopia de Infravermelho com Transformada de Fourier , Ativação Enzimática , Peróxido de Hidrogênio/química , Conformação Proteica , Desnaturação Proteica , Eletricidade Estática , Especificidade por Substrato
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