Synchrotron X-ray diffraction and absorption studies of CeM2X2 (M=Cu, Ni and X=Si, Ge) at high pressure

The equations of state of CeCu₂Si₂ and CeCu₂Ge₂ to about 60 GPa, as well as that of CeNi₂Ge₂ to 22 GPa and the valence state of Ce in CeCu₂Ge₂ to 20 GPa have been studied at room temperature in a diamond-anvil cell using synchrotron radiation sources. In each compound, the ambient-pressure phase (tetragonal ThCr₂Si₂-type structure) persisted to the highest pressure studied. The unit cell volumes of CeNi₂Ge₂ at ∼5 GPa and CeCu₂Ge₂ at ∼7 GPa, respectively, approached that of CeCu₂Si₂ taken at ambient pressure. From the equation-of-state data, the bulk modulus was derived to be 112.0±5.1 GPa for CeCu₂Si₂, 125.6±4.3 GPa for CeCu₂Ge₂, and 178.4±14.3 GPa for CeNi₂Ge₂. The valence state of Ce in CeCu₂Ge₂ remained trivalent throughout the pressure range investigated.     

Nuclear magnetic resonance study of strongly correlated superconductors

This paper introduces nuclear magnetic resonance works in the strongly correlated super-conductors: heavy-Fermion, high-T _C superconductors and Sr₂RuO₄. The analyses strongly support the spin-fluctuation-mediated superconductivity model in a high-T _C superconductor.     

Nonlinear resonances and self-excited oscillations of a rotor caused by radial clearance and collision

This paper investigates oscillations in a flexible rotor system with radial clearance between an outer ring of the bearing and a casing by experiments and numerical simulations. The mathematical model considers the collisions of the bearing with the casing. The following phenomena are found: (1) Nonlinear resonances of subharmonic, super-subharmonic and combination oscillation occur. (2) Self-excited oscillation of a forward whirling mode occurs in a wide range above the major critical speed. (3) Entrainment phenomena from self-excited oscillation to nonlinear forced oscillation occur at these nonlinear resonance ranges. Moreover, this study analyzes periodic solutions of the mathematical model by the Harmonic Balance Method (HBM). As the results, the nonlinear resonances of subharmonic oscillation and its entrainment phenomenon can be explained theoretically by investigating the stability of the periodic solutions. The influence of the static force and the bearing damping on these oscillation are also clarified.     

Forced proximity of nitroxide groups in pincer compounds with a xanthene spacer

We designed bisnitroxide compounds where the radical sites are located close to each other in a molecule. Two new pincer-type bisnitroxide compounds have been synthesized, involving xanthene-4,5-diyl as a spacer and tert-butyl phenyl nitroxides as arms. From the X-ray crystal structure analysis, the shortest intramolecular interatomic N?O and O?O distances respectively are 5.074(6) and 5.258(6) Å for the m,m′-derivative and 3.624(3) and 3.771(3) Å for the p,p′-derivative. The N?O distance in the latter satisfies the empirical criterion for possible dimerization/degradation reaction accompanied by dia-/paramagnetic transition. However, the magnetic study clarified paramagnetic behavior in all the temperature range. According to a singlet-triplet model, antiferromagnetic couplings were characterized with 2J/k_B = ?7.71(2) and ?8.83(4) K for the m,m′ and p,p′-derivatives, respectively. The present result suggests that a more flexible spacer is required for realization of possible dia-/paramagnetic transition.     

Synthesis,spectroscopic characterization,crystal structures,and theoretical studies of (<Emphasis Type="Italic">E</Emphasis>)-2-(2,4-dimethoxybenzylidene)thiosemicarbazone and (<Emphasis Type="Italic">E</Emphasis>)-2-(2,5-dimethoxybenzylidene)thiosemicarbazone

Two thiosemicarbazones, (E)-2-(2,4-dimethoxybenzylidene)thiosemicarbazone (24-MBTSC (1)) and (E)-2-(2,5-dimethoxybenzylidene)thiosemicarbazone (25-MBTSC (2)), derived from 2,4-dimethoxybenzaldehyde and 2,5-dimethoxybenzaldehyde, respectively, with thiosemicarbazide have been synthesized and their structures were characterized by elemental analyses, FT-IR, ¹H NMR spectroscopy, and X-ray single-crystal diffraction analysis. Molecular orbital calculations have been carried out for 1 and 2 by using an ab initio method (HF) and also density functional method (B3LYP) at 6-31G basis set. Compound 1 crystallizes in the monoclinic system, space group P2₁/c, with a = 8.1342(5) Å, b = 18.1406(10) Å, c = 8.2847(6) Å, β = 109.7258(17)°, V = 1150.75(12) Å³, and Z = 4, whereas compound 2 crystallizes in the orthorhombic system, space group Pbca, with a = 11.0868(6) Å, b = 13.1332(6) Å, c = 15.9006(8) Å, V = 2315.2(2) Å³, and Z = 8. The compounds 1 and 2 displays a trans-configuration about the C=N double bond.     

Communication: Synthetic Studies on Sialoglycoconjugates 25: Reactivity of Glycosyl Promoters in α-Glycosylation of N-Acetyl-Neuraminic Acid with the Primary and Secondary Hydroxyl Groups in the Suitably Protected Galactose and Lactose Derivatives

Development of an efficient α-glycoside synthesis of sialic acids is critically significant for the syntheses of sialoglycoconjugates, especially gangliosides which carry important biological functions¹ in biological systems. Previously, we demonstrated² a new α-glycosylation of sialic acids by use of dimethyl(methylthio)sulfonium triflate (DMTST)³ as the glycosyl promoter, the suitably protected glycosyl acceptors and the methyl 2-thioglycoside 1 of N-acetylneuraminic acid (Neu5Ac) as the donor in acetonitrile under kinetically controlled conditions, and accomplished⁴ the syntheses of a variety of gangliosides and their analogs.     

Synthetic Studies on Sialoglycoconjugates 95: Total Synthesis of Sulfated Glucuronyl Lactosaminyl Paraglobosides

ABSTRACT

3-O-Sulfo glucuronyl neolactohexanosyl ceramide derivatives (heptasaccharides) have been synthesized. Condensation of 2-(trimethylsilyl)ethyl 2,4,6-tri-O-benzyl-β-D-galactopyranoside (2) with 4-O-acetyl-3,6-di-O-benzyl-2-deoxy-2-phthalimido-β-D-glucopyranosyl trichloroacetimidate (1) gave the desired β-glycoside 3, which was converted into 2-(trimethylsilyl)ethyl O-(2-acetamido-3,6-di-O-benzyl-2-deoxy-β-D-glucopyranosyl)-(1→3)-2,4,6-tri-O-benzyl-β-D-galactopyranoside (4) via removal of the O-acetyl and N-phthaloyl groups, followed by N-acetylation. Glycosylation of 4 with O-(methyl 4-O-acetyl-2-O-benzoyl-3-O-levulinoyl-β-D-glucopyranosyluronate)-(1→3)-2,4,6-tri-O-benzoyl-α-D-galactopyranosyl trichloroacetimidate (5) using trimethylsilyl trifluoromethanesulfonate gave the target tetrasaccharide 6, which was transformed via removal of the benzyl group, O-benzoylation, removal of the 2-(trimethylsilyl)ethyl group and imidate formation into the tetrasaccharide donor 9. Glycosylation of 2-(trimethylsilyl)ethyl O-(2-acetamido-3,6-di-O-benzyl-2-deoxy-β-D-glucopyranosyl)-(1→3)-O-(2,4,6-tri-O-benzyl-β-D-galactopyranosyl)-(1→4)-2,3,6-tri-O-benzyl-β-D-glucopyranoside (10) with the imidate donor 9 using trimethylsilyl trifluoromethanesulfonate gave the desired heptasaccharide 11, which was transformed into the heptasaccharide imidate donor 14. Glycosylation of (2S, 3R, 4E)-2-azido-3-O-benzoyl-4-octadecene-1,3-diol (15) with 14 gave β-glycoside 16, which was transformed into the four target compounds, via reduction of the azido group, coupling with octadecanoic acid or tetracosanoic acid, selective removal of the levulinoyl group, O-sulfation, hydrolysis of the methyl ester group and O-deacylation.