Visible-light-sensitive photocatalytic reaction on chromium-containing mesoporous silica: selective partial oxidation of propane with molecular oxygen

The photocatalytic reactivities of chromium-containing mesoporous silica molecular sieves (Cr-HMS) under visible light irradiation have been investigated. Cr-HMS involves tetrahedral chromium oxide (Cr-oxide) moieties which are highly dispersed and incorporated in the framework of molecular sieve with two terminal Cr=O groups. In the presence of propane with molecular oxygen, a partial oxidation proceeded under visible light irradiation to produce acetone and acrolein, with high selectivity, while a complete oxidation proceeded under UV light irradiation mainly to produce CO₂. The charge-transfer excited state of the tetrahedral Cr-oxide moieties plays a significant role in the photocatalytic reactions.     

A convenient method for the preparation of α-vinylfurans by phosphine-initiated reactions of various substituted enynes bearing a carbonyl group with aldehydes

α-Vinylfurans were obtained by phosphine-initiated cyclization of various enynes bearing a carbonyl group at the ene end in the presence of various aldehydes, in moderate to high yields. The reaction may consist of 1,6-addition of phosphine to the enynes, ring closure, and Wittig reaction between the ylid resulting from cyclization and an aldehyde. Thus, various aldehydes were able to be used in the reaction. The reaction was influenced greatly by the substituents at the acetylene position (R¹) and the α-position of the carbonyl group (R³).     

Development of measuring magnetic Compton profiles by grazing incidence geometry

A novel technique of measuring a magnetic Compton profile using the grazing angle geometry against a sample surface (Grazing Incidence Magnetic Compton Profile) has been successively developed. Measurements of a magnetic moment and a magnetic Compton profile are possible for a Fe 200 nm film on a thick glass substrate. The estimated thinnest limit for measurements is 100 nm for a Fe film.     

Reversible formation of F+-centers over platinum promoted sulfated zirconia upon hydrogen treatment

Reversible formation of F⁺-centers was observed over platinum promoted sulfated zirconia in the presence and absence of hydrogen. The intensity of ESR signal of F⁺-centers was increased by treatment in He stream and it was decreased rapidly by supply of hydrogen in gas phase. This behavior seems to be related to proton spillover.     

A hybrid approach combining energy density analysis with the interaction energy decomposition method

We propose a new analysis technique for characterizing molecular interactions that combines an energy decomposition scheme, such as the Kitaura-Morokuma decomposition method, with energy density analysis, which partitions the total energy of the system into atomic contributions. The combined scheme, termed Interaction-EDA, enables us to estimate the local contribution of interaction energy components, such as electrostatic, exchange, polarization, and charge transfer. The evaluation of the local interaction energy is rather important in large systems. For a numerical assessment, the Interaction-EDA method is applied to the process of CO adsorption on Si(100) - (2 x 1) surface.     

Highly sensitive determination of haloperidol in human serum by capillary gas chromatography using a surface ionization detector

A method has been developed for highly sensitive determination of haloperidol in human serum involving a simple extraction procedure followed by gas chromatographic separation. Target components were separated from the extracting solvents with a Van den Berg type solventless sample injector before introduction Into a DB-1 capillary separation column. A surface ionization detector (SID), which has highly selective sensitivity for Substituted amines, was employed for quantitation using bromperidol as an internal standard. Chloroform proved to be the best extracting solvent, yielding a quantitative detection limit of 5 ng/ml (S/N = 2). Comparison of the response to target compounds obtained by the SID, FTD (flame thermionic detector), and FID (flame ionization detector) showed the SID to be superior.     

Supersonic jet fluorescence spectrometry of perylene and benzo[a]pyrene

A supersonic jet instrument for fluorescence spectrometry is described. It consists of a high-temperature free expansion nozzle for continuous sample introduction and a vacuum chamber equipped with a high-speed pumping system. Rotationally cooled spectra obtained with the supersonic jet are compared with gas-phase spectra measured at high temperature for perylene and benzo[a]pyrene molecules. Each component of the unresolved band structure in the high-temperature spectra was found to be composed of a rotational congestion of several vibrational bands. For a 1:1 mixture of perylene and benzo[a]pyrene, selective detection is possible by using supersonic jet spectrometry. The detection limit for perylene is 100 ng. The advantage of this technique over other low-temperature spectrometric methods based on Shpol'skii and matrix isolation effects are discussed.     

Is recombinant human granulocyte colony-stimulating factor (G-CSF) orally available in rats?

Oral availability of recombinant human granulocyte colony-stimulating factor (G-CSF) was investigated in rats by measuring the blood total leucocyte (BTL) counts. Oral test G-CSF solution was prepared with 10% HCO-60 (polyoxyethylated, 60 mumol, castor oil derivative), 1% DK ester (sugar ester) or 10% MYS-40 (polyethyleneglycol monostearate), in which the G-CSF concentration was 500 or 250 micrograms/ml. Each test solution was injected into the duodenum of three rats at the G-CSF dose level of 300 or 600 micrograms/kg, and BTL counts were monitored for 48 h. All of the test G-CSF solution raised the BTL levels within 24 h after injection. In particular, the HCO-60 solution increased the BTL levels over 2 times as compared to the predose level at 600 micrograms/kg dose and the effect was apparently dose-dependent. A short-term study suggested that the effect of G-CSF on the BTL level appeared at the fastest at about 5 h after administration of HCO-60 test solution, 300 micrograms/kg. In view of the pattern of BTL dynamics obtained after i.v. injection of HCO-60 solution at 25 and 50 micrograms/kg, the increase of BTL levels observed after oral administration of the HCO-60 solution is considered to be due to the orally supplied G-CSF.     

The first example of the stereoselective synthesis of 7 beta-carbamoyl-4,5alpha-epoxymorphinan via a novel and reactive gamma-lactone

7beta-Carbamoyl-4,5alpha-epoxymorphinans 5 were stereoselectively synthesized from the 7alpha-carboxylate intermediate 3 in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and amines under reflux conditions in mesitylene via a novel and reactive gamma-lactone 7. These were the first examples of the stereoselective syntheses of 7beta-substituted 4,5alpha-epoxymorphinans. The mechanism of the reaction process was elucidated as follows: 1) epimerization of 7alpha-carboxylate 3, 2) intramolecular lactonization of 7beta-carboxylate 6, and 3) aminolysis of the resultant gamma-lactone 7. The aminolysis of the isolated reactive gamma-lactone 7 with allylamine and the alcoholysis with MeOH in the presence of NaBH(4) proceeded at room temperature. The gamma-lactone 7 can be a useful intermediate for the preparation of 7beta-substituted 4,5alpha-epoxymorphinans that would be potent selective delta opioid receptor ligands. The stereoselective syntheses of the 7alpha-carbamoyl-4,5alpha-epoxymorphinans 9 from 7alpha-carboxylate 3 via 7alpha-carboxylic acid were also successful.