Reaction of arylmethanesulfonyl and styrylmethanesulfonyl chlorides with triethylamine

A series of arylmethanesulfonyl chlorides were treated with triethylamine in THF to give stilbenes in excellent yields. Workup of the mixtures below 10 °C permits isolation of stilbene episulfones which on warming decompose to yield the corresponding stilbenes stereospecifically. Application of the reaction to 9-fluorenylsulfonyl chloride affords bifluorenylidene, while trans-styrylmethanesulfonyl chloride gives 4,5-dihydro- 4,5-diphenylthiepin 1,1-dioxide and 1,6-diphenylhexatriene.     

High-spin states of145Sm

High-spin states of¹⁴⁵Sm were studied by using the²⁰Ne(¹³⁶Xe, α7n),¹³⁹La (¹⁰B, 4n) and¹³⁸Ba(¹³C,6n) reactions. The decay scheme of a high-spin isomer of¹⁴⁵Sm was established. The excitation energy and the spin-parity of the isomer were determined to be 8.8 MeV and (49/2⁺), respectively. The level scheme was extended up to the (65/2) state at 14.6 MeV. The experimental results were discussed comparing with the deformed independent particle model (DIPM) calculation.     

New low-energy RIB separator CRIB for nuclear astrophysics

An in-flight RIB separator at low energies, which is the first extensive separator at low energies, called CRIB, is just under construction at CNS. This consists of a double-achromatic magnetic separator, a window-less gas target, and a Wien filter. Some characteristics of the CRIB are described. Possible experimental plans are also discussed in our nuclear astrophysics project for the study of the explosive hydrogen burning process, especially on the onset mechanism. Received: 1 May 2001 / Accepted: 4 December 2001     

Mo-Au combo catalysis for rapid 1,3-rearrangement of propargyl alcohols into alpha,beta-unsaturated carbonyl compounds

The combination of Mo and cationic Au catalysts dramatically accelerated the rearrangement of diverse propargyl alcohols, which includes a short reaction time, mild conditions, and high product yields. A practical application to the highly challenging primary propargyl alcohols and the N-alkynyl amides is achieved.     

Design and synthesis of a novel ring-expanded 4′-thio-apio-nucleoside derivatives

The synthesis of a ring-expanded 4′-thio-apio-nucleoside derivative 4, designed to serve as a potential anti-HIV agent, is described. The epoxy alcohol derivative 10, prepared from 2-butene-1,4-diol, was converted to an allylsulfide derivative 13 in 3 steps. Ring-closing-metathesis of 13 gave the dihydrothiopyran derivative 20, which was further converted into sulphoxide 24. A Pummerer-type thioglycosylation reaction of 24 with a persilylated uracil derivative, followed by conversion to a cytosine derivative and deprotection, gave a racemic mixture of the ring-expanded 4′-thio-apio-nucleoside derivative 4 in good yield.     

Effects of introduction of α‐carboxylate,N‐methyl,and N‐formyl groups on intramolecular cyclization of o‐quinone amines: Density functional theory‐based study

o‐Quinone amines, which are relevant to various biological processes, can undergo spontaneous intramolecular cyclization (ring closure reaction by amino‐terminated hydrocarbon side chain) that deactivates them toward another possible reactions, that is, thiol binding. Density functional theory‐based calculation is employed for obtaining the potential energy curves along the C? N bond formation in the intramolecular cyclization of various o‐quinone amines, viz., dopaminequinone, dopaquinone, N‐methyl‐dopaminequinone, N‐formyl‐dopaminequinone, and the corresponding methylene‐inserted analogues. The activation barrier is decreased by introduction of α‐carboxylate and N‐methyl group whereas increased by introduction of N‐formyl group. A negative correlation between the activation barriers and the level of highest occupied molecular orbital is pointed out. Furthermore, the methylene‐inserted analogues show decreased activation barriers. This is explained by reduction of steric repulsion in the transition state.     

A practical ortho-rearrangement of silyl group of ortho-bromophenyl silyl ethers using magnesium(0)

A practical synthesis of ortho-silyl-substituted phenol from ortho-bromophenyl silyl ethers without using RLi is described. Various ortho-bromophenyl silyl ethers are treated with commercially available Mg turnings, which are easy to handle in air, and transfer of the silyl group to the ortho-position occurs in good to high yields. Selective mono-magnesiation of 2,6-dibromophenyl silyl ether is observed even in the presence of excess Mg, and ortho-bromo-6-silylphenol is obtained as the predominant product. The obtained ortho-silyl-substituted phenol is formylated with (CH₂O)_n/MgCl₂/Et₃N, and then condensation with a diamine leads to a silyl-substituted salen-type ligand in a good yield. This scheme is suitable for the large scale synthesis of silyl-substituted salen-type ligands bearing imine groups.     

Triacylglycerol/phospholipid molecular species profiling of fatty livers and regenerated non-fatty livers in cystathionine beta-synthase-deficient mice, an animal model for homocysteinemia/homocystinuria

Fatty liver is one of the typical manifestations in homocysteinemia/homocystinuria patients and their genetic animal model, mice lacking cystathionine ??-synthase (Cbs ^?/?). The vast majority of Cbs ^?/? die within 4?weeks after birth via yet unknown mechanisms, whereas a small portion survive to adulthood, escaping fatty degeneration of the liver during lactation periods, through regeneration. To investigate the molecular basis of such fatty changes, we analyzed lipid components in fatty livers of 2-week-old Cbs ^?/? and regenerated non-fatty livers of 8-week-old Cbs ^?/? survivors using a chip-based nanoESI (electrospray ionization)-MS system, which allows quantitative detection of triacylglycerol/phospholipid molecular species. Hepatic levels of all major triacylglycerol species were much higher in Cbs ^?/? than in wild-type mice at 2?weeks, although not at 8?weeks. Levels of some phospholipid species were either up- or downregulated in 2-week-old Cbs ^?/?; e.g. saturated (16:0 and 18:0) or mono-unsaturated (16:1 and 18:1) fatty acids-containing phosphatidylcholine/phosphatidylethanolamine species were upregulated, while poly-unsaturated fatty acids-containing phosphatidylcholine (18:2?C18:2 and 18:2?C20:5), phosphatidylethanolamine (18:1?C20:4), and phosphatidylinositol (18:0?C20:4) were downregulated. Capillary electrophoresis-MS analysis identified high-level accumulation of S-adenosylmethionine and S-adenosylhomocysteine in fatty livers of 2-week-old Cbs ^?/? but much less in non-fatty livers of 8-week-old Cbs ^?/?. Although hepatic S-adenosylmethionine/S-adenosylhomocysteine ratios were comparable between 2-week-old Cbs ^?/? and wild-type, global protein arginine methylation was disturbed in fatty livers of Cbs ^?/?. Our results suggest that cellular signaling mediated by altered phospholipid contents might be involved in pathogenesis of fatty liver in Cbs ^?/?C.     

Growth of gold nanorods in gelled surfactant solutions

Gold nanorods have been actively studied for new nanotechnological materials and industrial applications. It is well known that gold nanorods grow spontaneously in surfactant solutions, and a number of procedures for their preparation have been reported; however, the factors that determine the morphology have not been well understood. In this study, we observed the time series of the growth process of gold nanorods in gelled surfactant solutions by completely stopping the growth reaction. This growth process was compared to that in solution without gelation. The comparison indicates that the self-assembly of surfactant molecules affected the resulting shape, especially the short-axis length, of the nanorods. Small-angle neutron scattering (SANS) experiments revealed that the gelled solutions form lamellar structures, whereas nongelled systems form spherical micelles. On the bases of these results, we present a model showing that the short-axis length of gold nanorods is affected by a decrease in the spontaneous curvature of the outer surfactant layer and/or an increase in the bending modulus of the surfactant membrane neighboring the gold surface.