Neutron scattering studies on heavy-fermion superconductors

We review recent neutron scattering studies on uranium-based heavy-fermion superconductors. The coupling between magnetic and superconducting order parameters was observed in UPt₃, UPd₂Al₃, URu₂Si₂, and UNi₂Al₃. In UPd₂Al₃, the superconducting gap appears in the spin excitation spectra. These results are indicative of the strong interplay between magnetism and superconductivity. We also report the unusual behaviors of the weak antiferromagnetic ordering, the long-range magnetic correlation in UPt₃ at ultra-low temperatures, and the pressure-induced magnetic transition from the weak (0.02μ_B/U) to a high moment state (0.4μ_B/U) at 1.5 GPa in URu₂Si₂.     

Electronic structure of a polydiacetylene nanowire fabricated on highly ordered pyrolytic graphite

A molecular wire candidate, the polydiacetylene chain, fabricated in a substantial support layer of monomers self-assembled on a highly ordered pyrolytic graphite surface, was studied using scanning tunneling microscopy and spectroscopy. The density of states of individual polymers and constituent monomers were observed on the same surface, and then compared with the calculated results. The spectrum delineating the density of states of the polydiacetylene wire clearly reveals the theoretically predicted pi-band and band edge singularities of the one-dimensional polymer.     

An efficient chemical fixation of nitric oxide: convenient and practical synthesis of 1,2,3-oxadiazole 3-oxides

Nitric oxide reacts efficiently with alkynyllithium at low temperature producing 1,2,3-oxadiazole 3-oxides in good yields.     

Spatially inhomogeneous development of antiferromagnetism in URu2Si2: evidence from 29Si NMR under pressure

From 29Si NMR study, we present evidence for spatially inhomogeneous development of antiferromagnetic (AF) ordering below T(o) = 17.5 K in URu2Si2. In the pressure range between 3.0 and 8.3 kbar, we have observed the 29Si NMR lines arising from the AF region as well as the previously observed 29Si NMR line which correspond to the nonmagnetic region in the sample. The AF volume fraction is enhanced by applied pressure, whereas the magnitude of internal field at the Si site remains constant (910 Oe) up to 8.3 kbar. In the AF region, the ordered moment is about an order of magnitude larger than 0.03 mu(B)/U.     

Synthesis of topsentolides A2 and C2, and non-enzymatic conversion of the former to the latter

The first total synthesis of the marine-derived cytotoxin topsentolide A₂, which eventually culminated in its stereochemical determination, was accomplished in 17 steps from a known chiral alcohol. An improved synthesis of its congener, topsentolide C₂, from a synthetic intermediate of topsentolide A₂ was also performed by utilizing the Yamaguchi lactonization to construct its nine-membered lactone ring. Treatment of epoxide ring-containing topsentolide A₂ with HCl/MeOH brought about its quantitative conversion into topsentolide C₂.     

Synthesis of rumphellaone A via epoxy nitrile cyclization

The first enantioselective total synthesis of rumphellaone A, a cytotoxic 4,5-seco-caryophyllane isolated from the gorgonian coral Rumphella antipathies, has been achieved from a known olefinic alcohol by a 16-step sequence involving Stork's epoxy nitrile cyclization as the key step to concomitantly install a cyclobutane ring and three contiguous stereogenic centers contained in the molecule.