4f delocalization in Gd: inelastic x-ray scattering at ultrahigh pressure.

We present resonant inelastic x-ray scattering and x-ray emission spectroscopy results on Gd metal to 113 GPa which suggest Kondo-like aspects in the delocalization of 4f electrons. Analysis of the resonant inelastic x-ray scattering data reveals a prolonged and continuous delocalization with volume throughout the entire pressure range, so that the volume-collapse transition at 59 GPa is only part of the phenomenon. Moreover, the Lgamma1 x-ray emission spectroscopy spectra indicate no apparent change in the bare 4f moment across the collapse, suggesting that Kondo screening is responsible for the expected Pauli-like behavior in magnetic susceptibility.

Superconductivity and lattice instability in compressed lithium from Fermi surface hot spots.

The highest superconducting temperature Tc observed in any elemental metal (Li with Tc approximately 18-20 K at pressure 35-48 GPa) is shown to arise from increasingly strong electron-phonon coupling concentrated along intersections of Kohn anomaly surfaces with the evolving Fermi surface. First-principles linear response calculations of the phonon spectrum and spectral function alpha2F(omega) reveal very strong Q- and phonon-polarization dependence of coupling strength, resulting in values of in the observed range. The sharp momentum dependence of the coupling even for the simple Li Fermi surface indicates more generally that a fine Q mesh is required for precise evaluation of lamda.

New cubic phase of Li3N: stability of the N3- ion to 200 GPa.

Diamond-anvil cell experiments augmented by first-principles calculations have found a remarkable stability of the N(3-) ion in Li3N to a sixfold volume reduction. A new (gamma) phase is discovered above 40(+/-5) GPa, with an 8% volume collapse and a band gap quadrupling at the transition determined by synchrotron x-ray diffraction and inelastic x-ray scattering. gamma-Li(3)N (Fm3m, Li(3)Bi-like structure) remains stable up to 200 GPa, and calculations do not predict metallization until approximately 8 TPa. The high structural stability, wide band gap, and simple electronic structure make this N(3-) based system analogous to lower valency compounds (MgO, NaCl, Ne), meriting its use as an internal pressure standard.

First-order isostructural Mott transition in highly compressed MnO.

We present evidence for an isostructural, first-order Mott transition in MnO at 105+/-5 GPa, based on high-resolution x-ray emission spectroscopy and angle-resolved x-ray diffraction data. The pressure-induced structural and spectral changes provide a coherent picture of MnO phase transitions from paramagnetic B1 to antiferromagnetic distorted B1 at 30 GPa, to paramagnetic B8 at 90 GPa, and to diamagnetic B8 at 105+/-5 GPa. The last is the Mott transition, accompanied by a significant loss of magnetic moment, an approximately 6.6% volume collapse and the insulator-metal transition as demonstrated by recent resistance measurements.

Martensitic fcc-to-hcp transformation observed in xenon at high pressure.

Angle-resolved x-ray diffraction patterns of Xe to 127 GPa indicate that the fcc-to-hcp transition occurs martensitically between 3 and 70 GPa in diamond-anvil cells without an intermediate phase. These data also reveal that the transition occurs by the introduction of stacking disorder in the fcc lattice at low pressure, which grows into hcp domains with increasing pressure. The small energy difference between the hcp and the fcc structures may allow the two phases to coexist over a wide pressure range. Evidence of similar stacking disorder and incipient growth of an hcp phase are also observed in solid Kr.

Phase diagram of carbon dioxide: evidence for a new associated phase.

The stability of CO(2) phases has been investigated up to 50 GPa and 750 K by in situ Raman spectroscopy and visual observations using externally heated diamond-anvil cells. A new phase (CO(2)-II) exists above 20 GPa and 500 K, which can be quenched to ambient temperature. The vibrational spectrum of this new CO(2) polymorph suggests the dimeric pairing of molecules. Based on the present in situ data and previous laser-heating results, we present new constraints for the phase diagram of carbon dioxide to 50 GPa and 2000 K. We find that carbon dioxide exhibits dramatic changes, both in the molecular configuration and in the nature of intermolecular interaction at high pressures and temperatures.

CT features of primary colorectal signet-ring cell carcinoma.

PURPOSE: The purpose of this work was to evaluate the CT features of 15 patients with primary colorectal signet-ring cell carcinomas. METHOD: We retrospectively reviewed the CT scans of 15 patients (mean age 44 years) with pathologically proved colorectal signet-ring cell carcinoma. On CT, we evaluated the site and length of the tumor, bowel wall thickening patterns, perirectal or pericolic infiltration, the presence or absence of colonic obstruction, and metastasis to other organs. RESULTS: The tumors were located in the rectum in nine patients, the sigmoid colon in one, the hepatic flexure in one, the transverse colon in one, the ascending colon in two, and the cecum in one. The tumor length ranged from 4.0 to 10.0 cm (mean 6.1 cm) with mean thickness of 2.1 cm. CT showed concentric bowel wall thickening in all patients ("even" in 8 and "uneven" in 7), target appearance was noted in 4, perirectal or pericolic infiltrations were moderate to severe in 12, and colorectal obstruction was seen in 6. In the tumor spread patterns, lymphadenopathy was noted in 13, invasion to adjacent pelvic organs in 5, peritoneal carcinomatosis in 4, liver metastasis in 2, and periureteric metastasis in 1. CONCLUSION: Primary signet-ring cell colorectal carcinoma should be included for differential consideration when CT shows a long length of concentric bowel wall thickening and target sign, especially when such findings occur in the rectum and in young patients.

Nonlinear carbon dioxide at high pressures and temperatures.

A nonlinear molecular carbon dioxide phase IV was discovered by laser heating CO2-III (Cmca) between 12 and 30 GPa, followed by quenching to 300 K. The Raman spectrum of quenched CO2-IV exhibits a triplet bending mode nu2(O = C = O) near 650 cm (-1), suggesting a broken inversion symmetry because of bending. The 650 cm (-1) bending modes soften with increasing pressure, indicating an enhanced intermolecular interaction among neighboring bent CO2 molecules. At 80 GPa, the low-frequency vibron collapses into high-frequency phonons, and CO2-IV becomes an extended amorphous solid.

Phase transformations in carbon fullerenes at high shock pressures.

C(60) powders were shock-compressed quasi-isentropically and quenched from pressures in the range 10 to 110 GPa (0.1 to 1.1 Mbar). Recovered specimens were analyzed by Raman spectroscopy and optical microscopy. C(60) fullerenes are stable into the 13- to 17-GPa pressure range. The onset of a fast ( approximately 0.5 micros) reconstructive transformation to graphite occurs near 17 GPa. The graphite recovered from 27 GPa and about 600 degrees C is relatively well ordered with crystal planar domain size of about 100 A. Above 50 GPa a continuous transformation to an amorphous state is observed in recovered specimens. The fast transformation to graphite is proposed to occur by pi-electron rehybridization which initiates breakup of the ball structure and formation of the graphite structure at high density.

Crystals of modified bovine neurophysin II.

An enzymatically modified form of bovine neurophysin II has been crystallized in three unique crystal forms. The orthorhombic form crystallizes in space group P2(1)2(1)2 with a = 15.33 nm, b = 6.92 nm, c = 3.63 nm, with four molecules in the asymmetric unit. The monoclinic form crystallizes in space group P2(1) with a = 6.22 nm, b = 9.55 nm, c = 5.45 nm and beta = 110.2 degrees, with eight molecules in the asymmetric unit. The tetragonal form crystallizes in space group P4(1)2(1)2 or P4(3)2(1)2 with a = 14.1 nm and c = 14.2 nm, with twelve molecules in the asymmetric unit. We report here the crystallization conditions, as well as the crystal data.

Structure of a novel Bence-Jones protein (Rhe) fragment at 1.6 A resolution.

The crystal structure of Rhe, a lambda-type Bence-Jones protein fragment, has been solved and refined to a resolution of 1.6 A. A model fragment consisting of the complete variable domain and the first three residues of the constant domain yields a crystallographic residual RF value of 0.149. The protein exists as a dimer both in solution and in the crystals. Although the "immunoglobulin fold" is generally preserved in the structure, there are significant differences in both the monomer conformation and in the mode of association of monomers into dimers, when compared to other known Bence-Jones proteins or Fab fragments. The variations in conformation within monomers are particularly significant as they involve non-hypervariable residues, which previously were believed to be part of a "structurally invariant" framework common to all immunoglobulin variable domains. The novel mode of dimerization is equally important, as it can result in combining site shapes and sizes unobtainable with the conventional mode of dimerization. A comparison of the structure with other variable domain dimers reveals further that the variations within monomers and between domains in the dimer are coupled. Some possible functional implications revealed by this coupling are greater variability, induced fitting of the combining site to better accommodate antigenic determinants, and a mechanism for relaying binding information from one end of the variable domain dimer to the other. In addition to providing the most accurate atomic parameters for an immunoglobulin domain yet obtained, the high resolution and extensive refinement resulted in identification of several tightly bound water molecules in key structural positions. These water molecules may be regarded as integral components of the protein. Other water molecules appear to be required to stabilize the novel conformation.

Effect of baclofen enantiomorphs on the spinal trigeminal nucleus and steric similarities of carbamazepine.

The seemingly structurally different drugs, baclofen and carbamazepine, have a similar neurophysiologic effect on the cat spinal trigeminal nucleus and a similar clinical effect in the amelioration of trigeminal neuralgia pain. In this investigation, we report on the enhancement of segmental inhibition by carbamazepine and l-baclofen; d-baclofen produced no effect on segmental inhibition. Doses of l-baclofen one fifth its equivalent racemic dosage produced a much greater enhancement of segmental inhibition. d-Baclofen, when given prior to l-baclofen, blocked the effect of l-baclofen on segmental inhibition and the unconditioned response at previously effective doses. Pretreatment with d-baclofen also blocked the effect of subsequent carbamazepine on segmental inhibition, but had no effect on the unconditioned response. Crystallographic evaluation of carbamazepine and the enantiomorphs of baclofen revealed a surprisingly good fit of baclofen isomers to moieties of the carbamazepine molecule. The results suggest that the baclofen enantiomorphs and carbamazepine have a common mechanism of action in the cat spinal trigeminal nucleus, and that d-baclofen, though inactive, is capable of interfering with the effect of l-baclofen and to a lesser extent with carbamazepine.