Group separation of trivalent actinides and lanthanides by tertiary pyridine-type anion-exchange resin embedded in silica beads

The separation of trivalent actinides and lanthanides was studied by using newly developed tertiary pyridine-type anion-exchange resin embedded in silica beads. Chromatographic elution experiments were carried out by using a packed column of the new resin and methanol-hydrochloric acid solution as an effluent. We confirmed that the actinides were eluted well from the elution bands of lanthanides. Actinides and lanthanides were eluted according to the reverse order of their atomic number.     

Synthetic alpha-mannosyl ceramide as a potent stimulant for an NKT cell repertoire bearing the invariant Valpha19-Jalpha26 TCR alpha chain

A NKT cell repertoire is characterized by the expression of the Valpha19-Jalpha26 invariant TCR alpha chain (Valpha19 NKT cell). This repertoire, as well as a well-established Valpha14-Jalpha281 invariant TCR alpha(+) NKT cell subset (Valpha14 NKT cell), has been suggested to have important roles in the regulation of the immune system and, thus, is a major therapeutic target. Here, we attempted to find specific antigens for Valpha19 NKT cells. Valpha19 as well as Valpha14 NKT cells exhibited reactivity to alpha-galactosyl ceramide (alpha-GalCer). Thus, a series of monoglycosyl ceramides with an axially oriented glycosidic linkage between the sugar and ceramide moiety were synthesized and their antigenicity to Valpha19 NKT cells was determined by measuring their immune responses in culture with glycolipids. Comprehensive examinations revealed substantial antigenic activity for Valpha19 NKT cells by alpha-mannosyl ceramide.     

Novel self-assembled monolayers of disulfides with bicyclo[2.2.2]octane moieties of Au(111)

A series of disulfides containing bicyclo[2.2.2]octane moieties have been synthesised and their self-assembled monolayers (SAMs) on Au(111) have been characterized using scanning tunnelling microscopy (STM).     

Studies on pyrazines. 29 . High regioselective synthesis of chloropyrazines from 3-substituted pyrazine 1-oxides

Reaction of 3-methoxy- or 3-chloropyrazine 1-oxides with refluxing phosphoryl chloride in the presence of amine led to a high regioselective formation of 3-substituted 2-chloropyrazines. In contrast, the use of chloroacetyl chloride instead of phosphoryl chloride enabled different regioselectivity to yield 6-substituted 2-chloropyrazines, particularly 3-methoxycarbonylpyrazine 1-oxide was almost exclusively converted into methyl 6-chloropyrazinecarboxylate under the conditions without the amine.     

A new lignan from the seeds of Sphaerophysa salsula

A novel lignan: sphaerophyside SC was isolated from ethanolic extract of the seeds of Sphaerophysa salsula (Pall.) DC. The structure of the compound was elucidated mainly on the basis of the 1D NMR and 2D NMR data.     

Effective photoexcitation in gold nanowells based on localized surface plasmon

The localization of the surface plasmon (SP) field in nanospace using wavelength-sized gold wells prepared on a glass substrate and its application to excite fluorophores immobilized on the bottom surfaces have been studied.     

Synthesis and inversion barriers of undeca- and dodeca-substituted saddle shaped porphyrin complexes

Synthesis and barriers to inversion of a series of highly saddle shaped complexes are reported. The ΔG^≠ has decreased by 8 kJ mol⁻¹ at 243 K when the meso phenyl groups are replaced by bulkier 2,6-dichlorophenyl groups, and by 17 kJ mol⁻¹ when one of the peripheral ethyl groups is removed.     

Laser photolysis studies of the photochemical reactions of chromium(III) octaethylporphyrin and tetramesitylporphyrin complexes in toluene solution

A nanosecond laser photolysis study was carried out for the Cr(III) porphyrin complexes of 2,3,7,8,12,13,17,18-octaethylporphyrin, [Cr(OEP)(Cl)(L)], and of 5,10,15,20-tetramesitylporphyrin, [Cr(TMP)(Cl)(L)], in toluene containing water and an excess amount of L (L = axial ligand). The laser photolysis generates the triplet excited state of the parent complex as well as a five-coordinate complex, [Cr(porphyrin)(Cl)], produced by the photodissociation of the axial ligand L. The yields for the formation of the triplet state and the photodissociation of L are found to markedly depend on the nature of both L and porphyrin ligand. The five-coordinate [Cr(porphyrin)(Cl)] readily reacts with both H(2)O and L in the bulk solution to give [Cr(porphyrin)(Cl)(H(2)O)] and [Cr(porphyrin)(Cl)(L)], respectively. The axial H(2)O ligand in [Cr(porphyrin)(Cl)(H(2)O)] is then substituted by the ligand L to regenerate the original complex [Cr(porphyrin)(Cl)(L)]. In principle, the substitution reaction takes place by the dissociative mechanism: the first step is the dissociation of H(2)O from [Cr(porphyrin)(Cl)(H(2)O)], followed by the reaction of the five-coordinate [Cr(porphyrin)(Cl)] with the ligand L to regenerate [Cr(porphyrin)(Cl)(L)]. The rate constants for this ligand substitution reaction are found to exhibit bell-shaped ligand concentration dependence. The detailed kinetic analysis revealed that both ligands L and H(2)O in toluene make a hydrogen bond with the axial H(2)O ligand in [Cr(porphyrin)(Cl)(H(2)O)] to yield dead-end complexes for the substitution reaction. The reaction mechanisms are discussed on the basis of the substituent effects of the porphyrin peripheral groups and the kinetic parameters determined from the temperature dependence of the rate constants.     

Geometric indices and the Alexander polynomial of a knot

It is well-known that any Laurent polynomial satisfying and is the Alexander polynomial of a knot in . We show that can be realized by a knot which has the following properties simultaneously: (i) tunnel number 1; (ii) bridge index 3; and (iii) unknotting number 1.