Determination of midazolam and its metabolite as a probe for cytochrome P450 3A4 phenotype by liquid chromatography-mass spectrometry

This study demonstrated the analysis of midazolam and its metabolites by liquid chromatography-mass spectrometry (LC-MS) with a sonic spray ionization (SSI) interface. The analytical column was a YMC-Pak Pro C18 (50 mm x 2.0 mm i.d.) using 10 mM ammonium acetate (pH 4.8)-methanol (1:1) at a flow rate of 0.2 ml min(-1). The drift voltage was 100 V. The sampling aperture was heated at 110 degrees C and the shield temperature was 230 degrees C. The lower limits for the detection of midazolam and 1'-hydroxymidazolam were 26.3 and 112.76 pg injected, respectively. The calibration curves for midazolam and 1'-hydroxymidazolam were linear in the range of 0.1-5 microg ml(-1). Within-day relative standard deviations was less than 7%. The method was applied to the determination of midazolam in monkey plasma, and the analysis of midazolam and its metabolites in an in vitro study with recombinant cytochrome P450 (CYP) 3A4. This method is sufficiently sensitive and useful to elucidate the kinetics of midazolam metabolite formation. We also investigated the effect of propofol on the metabolism of midazolam using recombinant CYP3A4. Propofol competitively inhibited the metabolism of midazolam to 1'-hydroxymidazolam by CYP3A4.     

A new class of rhodamine luminophores: design, syntheses and aggregation-induced emission enhancement

A new class of rhodamine luminophores, 3',3'-bis(oxospiroisobenzofuran)-3,7-bis(dialkylamino)benzopyrano-xanthene derivatives (ABPX), have been successfully developed. The emission behavior of ABPX series is directly opposite to the concentration quenching of conventional rhodamine dyes. ABPX series exhibit aggregation-induced emission enhancement (AIEE).     

Formation of n-alkyl-n(1-hydroperoxyalkyl)nitrosamines from n-alkyl-n-(1-acetoxyalkyl)nitrosamines

N-alkyl-N-(1-hydroperoxyalkyl)nitrosamines were prepared by treatment of the corresponding 1-acetoxyalkyl nitrosamines with hydrogen peroxide in acetic acid through an acid-catalyzed nucleophilic substitution.     

Photochemical modification of diamond films: introduction of perfluorooctyl functional groups on their surface

Photolysis of perfluoroazooctane with diamond films led the chemical modification of the surface to introduce perfluorooctyl functional groups, confirmed by means of Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and time-of-flight secondary ion mass spectrometry measurements. Diamond films modified with fluorine moieties showed improved frictional property and reduction of surface energy, as evaluated by contact angle to water, compared with a pristine diamond film. The contact angle and friction coefficient of chemically modified diamond film are 118 degrees and 0.1, respectively. The results of the value of the contact angle depending on irradiation times are consistent with those of the F/C ratio of fluorinated diamond films by monitoring with XPS.     

Fusaspirols A-D,novel oxaspirol derivatives isolated from Fusarium solani B-18

Four novel compounds with γ-methylidene-spirobutanolide core, fusaspirols A-D, were isolated from the brown rice culture of Fusarium solani B-18. Their structures were established by extensive spectroscopic analyses of 1D/2D-NMR, HRESITOFMS, and chemical derivatization. The absolute configurations of secondary alcohols in fusaspirols A and D were determined using modified Mosher's ester method. Fusaspirol A and 4,9-di-O-acetylfusaspirol A activated a signaling pathway in osteoclastic differentiation of murine macrophage derived RAW264.7?cells.     

Charge number effect on the miscibility of inorganic salt and surfactant in adsorbed film and micelle: Inorganic salt-dodecylammonium chloride mixtures

The effect of inorganic salts with different charge numbers of cations on the adsorption and micelle formation of dodecylammonium chloride (DAC) was clarified by applying the thermodynamic treatment of surfactant mixtures to mixtures of DAC with calcium and lanthanum chlorides and comparing the results with those of the sodium chloride-DAC mixture in the previous study. Surface tension of aqueous solutions of the salt-DAC mixture was measured as a function of the total molality of the mixture and the mole fraction of DAC in the mixture at 298.15 K under atmospheric pressure. Judging from the phase diagrams of adsorption and micelle formation obtained from the surface tension measurement, dodecylammonium cations expel inorganic cations from the adsorbed film and micelle and the repulsive interaction between dodecylammonium and inorganic cations increases with increasing charge number of the inorganic cation.     

Morphology and size-controlled synthesis of silver nanoparticles in aqueous surfactant polymer solutions

We have employed a number of reducing and capping agents to obtain Ag(0) metallic nanoparticles of various sizes and morphologies. The size and morphology were tuned by selecting reducing and capping agents. Spherical particles of 15 and 43 nm diameter were obtained when 1 wt% aqueous starch solution of AgNO₃ precursor salt was reduced by d(+)-glucose and NaOH, respectively, on heating at 70 °C for 30 min. Smaller size particles obtained in the case of d(+)-glucose reduction has been attributed to the slow reduction rate by mild reducing agent d(+)-glucose compared to strong NaOH. Conducting the reduction at ambient temperature of silver salt in liquid crystalline pluronic P123 and L64 also gave spherical particles of 8 and 24 nm, respectively, without the addition of any separate reducing agent. NaOH reduction of salt in ethylene glycol (11 g)/polyvinyl pyrolidone (PVP; 0.053 g) mixture produced large self-assembled cubes of 520 nm when smaller (26–53 nm) star-shaped sharp-edged structures formed initially aggregated on heating the preparation at 190 °C for 1 h. Increasing the amount of PVP (0.5 g) in ethylene glycol (11 g) and heating at 70 °C for 30 min yielded a mixture of spherical and non-spherical (cubes, hexagons, pentagons, and triangle) particles without the addition of an extra reducing agent. Addition of 5 wt% PVP to 1 wt% aqueous starched solution resulted in the formation of a mixture of spherical and anisotropic structures when solution heated at 70 °C for 1 h. Homogeneous smaller sized (29 nm) cubes were synthesized by NaOH reduction of AgNO₃ in 12.5 wt% of water-soluble polymer poly(methyl vinyl ether) at ambient temperature in 30 min reaction time.     

Photochemical electron transfer through [corrected] the interface of hybrid films of titania nano-sheets and mono-dispersed spherical mesoporous silica particles

Photochemical Electron Transfer (ET) between an organic dye, the porphyrin derivative TMPyP, and an electron acceptor, methyl viologen MV2+, have been investigated at the interface of two different inorganic films, i.e., layered titania nano-sheets (TNS) and a monolayer film of spherical and mono-dispersed mesoporous silica (sMPS) particles (ca. 0.5 microm). TMPyP ions were intercalated within the sMPS nano-cavities to form (TMPyP-sMPS) while MV2+ ions were intercalated into the TNS interlayers to form (MV2+-TNS). The (TMPyP-sMPS) and (MV2+-TNS) films were then stacked on a silica substrate in this order to form a (MV2+-TNS)/(TMPyP-sMPS) film and, upon UV light irradiation, ET could be induced. However, when this film was stacked inversely, i.e., for the (TMPyP-sMPS)/(MV2+-TNS) films on a silica substrate, no photoinduced ET were observed. Interestingly, however, even for this photo-inactive inversely stacked film, ET could be generated by inserting a gold vapor-deposited layer between the (MV2+-TNS) and (TMPyP-sMPS) films. The conjugation conditions at the interface of the inversely stacked (TMPyP-sMPS)/(MV2+-TNS) hybrid film were, thus, confirmed to strongly affect the photoinduced electron transfers and their efficiencies.     

Construction of macrocyclic structure using conformational properties of secondary and tertiary aromatic amides

A large macrocyclic compound with six para-phenylene rings and six amide moieties, which are alternately secondary and tertiary, was synthesized. In a stepwise synthesis, the final cyclization step was successful because a combination of three tertiary amides, which prefer a cis conformation, and two linear secondary amides would arrange both amino and carboxyl ends close to each other, while various sizes of macrocyclic compounds including the target cyclic trimer were generated in one-pot synthesis where three secondary amide bonds were formed.