Reaction of azole condensed quinoxaline N-oxides with acetic anhydride

The reaction of 7-chlorotetrazolo[1,5-α]quinoxaline 5-oxide 6a with acetic anhydride gave 7-chloro-5-(7-chlorotetrazolo[1,5-α]quinoxalin-4-yl)-4,5-dihydro-4-oxotetrazolo[1,5-α]quinoxaline 7a , while the reaction of 7-chloro-1,2,4-triazolo[4,3-α]quinoxaline 5-oxide 6b with acetic anhydride afforded 7-chloro-5-(7-chloro-1,2,4-triazolo[4,3-α]quinoxalin-4-yl)-4,5-dihydro-4-oxo-1,2,4-triazolo[4,3-α]quinoxaline 7b and 7-chloro-4,5-dihydro-4-oxo-1,2,4-triazolo[4,3-α]quinoxaline 8b . The reaction of compound 6a or 6b with acetic anhydride/acetic acid provided 7-chloro-4,5-dihydro-4-oxo-tetrazolo[1,5-α]quinoxaline 8a or compound 8b , respectively.     

Effect of surface covering of lactose carrier particles on dry powder inhalation properties of salbutamol sulfate

The effect of the surface covering of lactose carrier particles on the dry powder inhalation properties of salbutamol sulfate was investigated. Lactose carrier surfaces were covered with sucrose tristearate (J-1803F) by a high-speed elliptical-rotor-type powder mixer (Theta-Composer). In the present study, drug/carrier powder mixtures were prepared consisting of micronized salbutamol sulfate and lactose carriers with various particle surface conditions prepared by surface covering. These powder mixtures were aerosolized by a Jethaler), and the in vitro inhalation properties of salbutamol sulfate were evaluated by a twin impinger. Compared with the powder mixed with uncovered lactose carrier, the in vitro inhalation properties of the powder mixture prepared using the surface covering lactose carrier were significantly different, showing that the in vitro inhalation properties of salbutamol sulfate were improved. In vitro inhalation properties increased with the percentage of J-1803F added. Using this surface covering system would thus be valuable for increasing the inhalation properties of dry powder inhalation with lactose carrier particles.     

Influence of storage humidity on the in vitro inhalation properties of salbutamol sulfate dry powder with surface covered lactose carrier

The influence of storage humidity on the in vitro inhalation properties of salbutamol sulfate dry powder with surface covered lactose carrier was investigated. In the present study, drug/carrier powder mixtures were prepared consisting of micronized salbutamol sulfate and lactose carriers with different particle surface conditions prepared by surface covering. Lactose carrier surfaces were covered with vegetable magnesium stearate (Mg-St-V) by a high-speed elliptical-rotor-type powder mixer (Theta-Composer). These powder mixtures were aerosolized by a Jethaler), and the in vitro inhalation properties of salbutamol sulfate were evaluated by a twin impinger. Compared with the powder mixed with uncovered lactose carrier, the in vitro inhalation properties of the powder mixture prepared using the surface covered lactose carrier were little decreased with increased in relative humidity (RH), showing that the in vitro inhalation properties of salbutamol sulfate were improved at high RH. Using this surface covering technique would thus be valuable for storage humidity of dry powder inhalation (DPI) with lactose carrier particles.     

Solvation effects in near-critical binary mixtures

A Ginzburg-Landau theory is presented to investigate solvation effects in near-critical polar fluid binary mixtures. Concentration dependence of the dielectric constant gives rise to a shell region around a charged particle within which solvation occurs preferentially. As the critical point is approached, the concentration has a long-range Ornstein-Zernike tail representing strong critical electrostriction. If salt is added, strong coupling arises among the critical fluctuations and the ions. The structure factors of the critical fluctuations and the charge density are calculated and the phase transition behavior is discussed.     

Tandem radical reactions and ring-closing metathesis. Application in the synthesis of cyclooctenes

[reaction: see text] Fumarate- and acrylate-substituted oxazolidinones undergo tandem radical reaction to form dienes in moderate to good yields. The resulting dienes provide cyclooctenes in moderate to good yields after ring-closing metathesis (RCM). The role of the carbon backbone substituents and other variables in the efficiency of the eight-membered ring formation is discussed.     

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.     

Structural analysis of amylose tris(3,5-dimethylphenylcarbamate) by NMR relevant to its chiral recognition mechanism in HPLC

The structural analysis of amylose tris(3,5-dimethylphenylcarbamate) (ADMPC) was performed by NMR spectroscopy using a sample with a lower degree of polymerization in order to understand the chiral recognition mechanism when it was used as a chiral stationary phase (CSP) in high-performance liquid chromatography (HPLC). ADMPC exhibited chiral discrimination for many enantiomers, including 1-(9-anthryl)-2,2,2-trifluoroethanol (1) and 1,1'-bi-2-naphthol (2) in both NMR and HPLC. A good agreement was observed between the HPLC and NMR results when chloroform was employed as the common solvent. The structure of ADMPC in solution was investigated by NMR using the 2D NOESY technique coupled with computer modeling, and a left-handed 4/3 helical structure was obtained as the most probable one. The binding geometry between ADMPC and the enantiomers of 1 was also investigated by (1)H NMR titration. On the basis of these results combined with molecular modeling, a rational model to explain the chiral discrimination mechanism of 1 on ADMPC was proposed.     

The effect of the steric hindrance on metallic cation conduction in polymer electrolytes

2,6-Di-t-butylphenol and oligo(ethylene oxide) bound covalently to polyisocyanate were synthesized and characterized. The ionic conductivities of their Li, Na, and K phenolates were studied at various temperatures. The conductivities were in the range of 10^?7?10^?5 S/cm at 30°C. The conductivity of Na and K salts was approximately 10² greater than that of the Li salts. The t-butyl groups serve to dissociate K and Na ions from the phenoxide. The cations, therefore, are more mobile as a result increasing the conductivity. The temperature dependence of ionic conductivity suggests that the migration of ions is controlled by segmental motion of the polymer, shown by linear curves obtained in Vogel–Tammann–Fulchere plots. The polyisocyanate backbone is a rather stiff structure, however, a flexible oligo(ethylene oxide) side chain forms complexes with metal ion. Since the ion transport is associated with the local movement of polymer segments, the rigidity of the polymer backbone does not have much influence on the ion mobility.     

Synthesis and tautomeric behavior of 3-(pyrazolylhydrazonomethyl)-2-oxo-1, 2-dihydroquinoxalines. Specification of hydrazone imine and diazenyl enamine forms

3-(Pyrazolylhydrazonomethyl)-2-oxo-1, 2-dihydroquinoxalines were synthesized, and their tautomer ratios between hydrazone imine and diazenyl enamine forms were specified by pmr spectral data.     

Second-order nonlinear optical properties from poled silicate channel-waveguide

Thin film waveguides of germanosilicate glass are fabricated byrf-sputtering. Second-order nonlinearity ofd ₃₃=3.2 pm/V is obtained from electrically poled film, and the lifetime of the nonlinearity is found to be310 years. The poled channel-waveguide is prepared and the Cerenkov-type phase-matched frequency doubling is successfully observed.