Major-to-ultratrace elements in bone-marrow fluid as determined by ICP-AES and ICP-MS.

The major-to-ultratrace elements in human bone-marrow fluid were determined by ICP-AES (inductively coupled plasma atomic emission spectrometry), and ICP-MS (inductively coupled plasma mass spectrometry). The bone-marrow fluid sample was centrifuged prior to acid digestion to exclude the bone piece from bone marrow, and then digested with nitric acid. As a result, 20 elements could be determined over the concentration range from 1610 microg g(-1) for Na to 0.00043 microg g(-1) for W. It was found that Fe, Zn and Sb were enriched by ca. 264-, 7- and 15-fold, respectively, in bone-marrow fluid, compared to those in human blood serum. Alkali metals (K, Rb, Cs), except for Na, were also significantly enriched in bone-marrow fluid. Furthermore, the concentrations of various elements, such as Fe, P, Al, Zn, Cu, Se, Zr, Sn, Ag and W, were significantly higher than those in open seawater.     

Formation of metallic NbSe2 nanotubes and nanofibers

We succeed in synthesizing NbSe₂ nanotubes along with nanofibers by chemical vapor transportation. They are stable crystalline systems and can be synthesized reproducibly in a nearly equilibrium reacting process. We have investigated these nanosize structures of NbSe₂ by transmission electron microscopy and electron diffraction. Both of the structures have a similar size of 100–200 nm in diameter. While nanotubes consist of rolled-up NbSe₂ layers, nanofibers are a pile of thin flat layers. We propose a mechanism of the formation of NbSe₂ nanotubes and nanofibers on the basis of deseleniditive transition from a NbSe₃ fiber-shaped crystal. We also measured electrical resistance of the nanofibers with conductive atomic force microscopy and demonstrated that the material show metallic behavior at room temperature.     

Purines. LII. Synthesis and biological evaluation of 8-methylguanine 7-oxide and its 9-arylmethyl derivatives.

The synthesis of 8-methylguanine 7-oxide (3) was accomplished via a "phenacylamine route", which started from condensation of alpha-(4-methoxybenzylamino)propiophenone (6), prepared by coupling of alpha-bromopropiophenone (4) and 4-methoxybenzylamine (5), with 2-amino-6-chloro-5-nitro-4(3H)-pyrimidinone (7) and proceeded through cyclization of the resulting phenacylaminopyrimidinone (8) and removal of the 4-methoxybenzyl group. The N-oxide 3 and its 9-arylmethyl derivatives 9 and 11 showed only very weak antileukemic activity and no antimicrobial activity.     

Determination of rare earth elements in human blood serum by inductively coupled plasma mass spectrometry after chelating resin preconcentration

The determination of all rare earth elements (REEs) in human blood serum by inductively coupled plasma mass spectrometry (ICP-MS) was performed with the aid of chelating resin (Chelex 100) preconcentration after acid digestion with HNO3 and HClO4. When chelating resin preconcentration was carried out at room temperature, the recoveries of heavy REEs were lower than those of light REEs because of their stable complex formation with residual organic compounds remaining in the digested serum solution. These problems were overcome by heating the solution at 80 degrees C during the chelating resin preconcentration process. As a result, the recoveries for all REEs were improved to 92-102% in the case of a concentration factor of 4, where the analytical detection limits for REEs were below 0.2 x 10(-12) g ml-1. Consequently, all REEs in individual human blood sera collected from five healthy volunteers could be determined by ICP-MS with good precision. The concentrations of REEs in human blood serum were extremely low, in the range from ca. 1 x 10(-12) g ml-1 of Eu to ca. 230 x 10(-12) g ml-1 of Ce.     

Structural features of aliphatic N-nitrosamines of 7-azabicyclo[2.2.1]heptanes that facilitate N-NO bond cleavage

N-Nitrosamines can be considered as potential nitric oxide (NO)/nitrosonium ion (NO(+)) donors. However, the relation of the structures of N-nitrosamines, in particular of aliphatic N-nitrosamines, to the characteristics of release of NO or NO(+) remains unclear. Here we show that aliphatic N-nitrosoamines of 7-azabicyclo[2.2.1]heptanes can undergo heterolytic N-NO bond cleavage. On the basis of the observation of reduced rotational barriers of the N-NO bonds in solution and nitrogen-pyramidal structures of the N-nitroso group in the solid state, we postulate that N-NO bond cleavage of N-nitrosamines is enhanced by a reduction of the resonance in the N-NO group. Computational studies suggest that these structural features of the N-nitrosamines of 7-azabicyclo[2.2.1]heptane are derived from angle strain imposed on the CNC angles.     

Adsorption Isotherm of Water Vapor and Its Large Hysteresis on Highly Ordered Mesoporous Silica

The first and second adsorption–desorption isotherms of water vapor on a new mesoporous material derived from kanemite have been measured. The isotherms show unusual type V isotherms and large hysteresis. The type V isotherms, which have never been observed for the other adsorbates, suggest that the mesoporous material has a hydrophobic surface, although the hydrophobicity decreased after treatment with water vapor because of rehydration of the surface. The significantly large hysteresis could be explained by the difference in contact angle between adsorption and desorption.     

Decomposition of Co2TiO4 spinel below 1000 K

Co₂TiO₄ spinel was found to decompose to the mixture of CoTiO₃ ilmenite and Co₃O₄ spinel below 1000 K. The decomposition rate was the larger for the sample ground for the longer period. It showed a maximum around 870–920 K which seemed to appear from the balance between the rate increase by diffusion and the decrease of nucleation probability with temperature. The thermodynamical consideration supported the experimental results.     

Mechanism of thermal 2+2 cycloaddition reactions between electron-donors and electron-acceptors : Reactions of heteronuclear cycloaddends,CO groups

The 2 + 2 cycloaddition and “ene” mechanisms previously proposed for electron-accepting homonuclear cycloaddends have been found to hold for heteronuclear ones. Only a difference recognized between them consists in the relative stability of intermediate species. We think the proposed mechanism including its variations can cover thermal 2 + 2 cycloaddition reactions between donors and acceptors and “ene” reactions.     

A novel synthesis of (+)-biotin from L-cysteine

(+)-Biotin (1) was synthesized in 25% overall yield over 11 steps from L-cysteine. The contiguous asymmetric centers at C-3a and C-6a were formed through a novel and highly stereoselective Lewis base-catalyzed cyanosilylation of alpha-amino aldehyde 3 to provide anti-O-TMS-cyanohydrin 4 with high stereoselectivity and in high yield (anti/syn = 92:8, 96%). Treatment of 4 with a di-Grignard reagent, 1,4-bis(bromomagnesio)butane, followed by carbon dioxide, efficiently installed the 4-carboxybutyl chain at C-4 to give keto acid 5. The final cyclization to bicyclic compound 7b, a precursor to 1, was realized by a palladium-catalyzed intramolecular allylic amination of cis-allylic carbonate 6b that was elaborated from 5.     

Measurement of acid-catalyzed isomerization of unsaturated aldehyde-2,4-dinitrophenylhydrazone derivatives by high-performance liquid chromatography analysis

Aldehyde-2,4-dinitrophenylhydrazones exist as (E)- and (Z)-geometrical isomers, and adventitious isomerization during sample preparation can cause analytical errors. Purified alkenal-2,4-dinitrophenylhydrazone derivatives comprise only the (E)-isomer. However, partial isomerization to the (Z)-isomer occurs upon addition of acid to attain an equilibrium isomer ratio. The UV-visible spectral properties of the isomers differ; the (Z)-isomer exhibiting a 6-10 nm lower absorption maximum compared to the (E)-isomer. Alkenal-2,4-dinitrophenylhydrazones having a CC double bond at the 2- or 3-position of the alkenal exhibited similar absorption maxima with an equilibrium isomer ratio (0.035) that was much lower than those of other alkenals. The CC double bond at the 3-position migrates to a position of conjugation with the CN double bond during hydrazone synthesis to form a stabilized molecular structure. Alkenal-2,4-dinitrophenylhydrazones having a double bond at the 4-position or greater exhibited a similar absorption maxima equilibrium isomer ratio (0.14) to alkanal-2,4-dinitrophenylhydrazones. The quantitative analysis of carbonyl compounds in air or water using DNPH is usually conducted in the presence of an acid catalyst. Consequently, the solution of the direct extract prepared for HPLC or GC analysis contains both (E)- and (Z)-isomers.