Reactions of 2-amino-, 2-alkylamino-, and 2-piperidino-1-azaazulenes with aryl and chlorosulfonyl isocyanates

Reaction of 2-amino-1-azaazulene with phenyl isocyanate gave 3-phenyl-2H-3,4-dihydro-1,3,4a-triazabenz[5,4-a]azulene-2,4-dione. Reactions of 2-alkylamino-1-azaazulenes with aryl isocyanates gave 2-(N-ethyl-N′-arylureido)-1-azaazulenes initially, which rearranged to N-aryl-2-alkylamino-1-azaazulene-3-carboxamides and successive reaction with another molar amount of aryl isocyanate furnished uracil-fuzed 1-azaazulenes. Reaction of 2-piperidino-1-azaazulene with aryl isocyanate gave N-aryl-2-piperidino-1-azaazulene-3-carboxamide. Reaction of 2-(substituted amino)-1-azaazulenes with chlorosulfonyl isocyanate gave 3-cyano- and 3-chloro-2-(substituted amino)-1-azaazulenes.     

Determination of phosphatidylglycerol in amniotic fluid for prediction of foetal lung maturity by microbore-column liquid chromatography

Phosphatidylglycerol (PG) has been determined in amniotic fluid from 55 patients by using a microbore-column liquid chromatographic system. The present analysis time is 1 h 40 min for pretreatment of amniotic fluid and 20 min for a chromatographic run. From 2 ml of amniotic fluid, the PG content has been determined between 1.0 and 0.05 mg/dl. The detection limit of PG is 10 ng. As the injection volume (0.5 microliter) is small, repeated analyses are possible if necessary. It is concluded that, in the case of PG values over 0.10 mg/dl, a mother can deliver an infant without respiratory distress syndrome. This method is useful not only for the prenatal evaluation of lung maturity, but also for the assessment of any therapeutic effect.     

Constituents of seed of Malva verticillata. VII. Structural features and reticuloendothelial system-potentiating activity of MVS-I, the major neutral polysaccharide.

The structural features of MVS-I, the major neutral polysaccharide isolated from the seeds of Malva verticillata L., were elucidated by controlled Smith degradation, methylation analysis, partial acid hydrolysis and enzymic degradation studies. It has a backbone chain composed of beta-1,3-linked D-glucose and D-galactose residues having branches composed of alpha-1,5-linked L-arabinosyl beta-1,4-linked D-galactose and of beta-1,4-linked D-galactosyl beta-1,3-linked D-glucose residues at position 6 of a part of D-galactose units as side chains. MVS-I showed remarkable reticuloendothelial system-potentiating activity in a carbon clearance test.     

Preparation and properties of inhalable nanocomposite particles: effects of the size, weight ratio of the primary nanoparticles in nanocomposite particles and temperature at a spray-dryer inlet upon properties of nanocomposite particles

Nanoparticles are expected to be applicable to inhalation as carrier but there exist disadvantages because of their size. Their deposition dose to the lung will be small. To overcome this problem and utilize nanoparticles for inhalation, we have prepared nanocomposite particles as drug carriers targeting lungs. The nanocomposite particles are prepared as drug-loaded nanoparticles–additive complex to reach deep in the lungs and to be decomposed into nanoparticles when they deposit into lung. In this study, we examined the effect of preparation condition – inlet temperature, size of primary nanoparticles and weight ratio of primary nanoparticles – on the property of nanocomposite particles.

When the size of primary nanoparticles was 400 nm and inlet temperature was 90 °C, only the nanocomposite particles containing between 45 and 55% of primary nanoparticles could be decomposed into nanoparticles in water. On the other hand, when the inlet temperature was 80 °C, nanocomposite particles were decomposed into nanoparticles independent of the weight ratio of primary nanoparticles. Also, the aerodynamic diameter of the nanocomposite particles was between 1.5 and 2.5 μm, independent of the weight ratio of primary nanoparticles.

When the size of primary nanoparticles was 200 nm and inlet temperature was 70 °C, nanocomposite particles were decomposed into nanoparticles independent of the weight ratio of primary nanoparticles. Also, the aerodynamic diameters of them were almost 2.0 μm independent of the weight ratio of primary nanoparticles. When the nanocomposite particles containing nanoparticles with the size of 200 nm are prepared at 80 °C, no decomposition into nanoparticles was observed in water.

Fine particle values, FPF, of the nanocomposite particles were not affected by the weight ratio of primary nanoparticles when they were prepared at optimum inlet temperature.     

Preparation of ultrafiltration membranes of HCEC and CTA blend, and studies of resistance to microbiological degradation and other properties

Blends of high cyanoethylated cellulose (HCEC) (D_s = 2.5) and cellulose triacetate (CTA) (D_s = 2.8) were prepared for evaluation as ultrafiltration membranes. The rejection R_a and water permeability (P_w) of these membranes with respect to bovine serum albumin (BSA), were measured with the variations in composition and conditions of preparation. It was possible to define the reaction conditions and compositions that offered optimum performance with respect to R_a and J_w, and resistance to microbial degradation as well as acid and alkali hydrolysis. The morphology of membrane thereby obtained was characterized by scanning electron microscopy (SEM). The UF membrane cast from a solution of 1,4-dioxane: 12.5 g, acetone: 12.5 g, HCEC: 1.5 g, CTA: 3 g and PEG (MW = 1000): 10.5 g showed the optimum performance of P_w = 10 × 10⁻¹⁰ m³/(m² s Pa), BSA Rejection (R_a) = 99%, (J_w = 17.3 m³/(m² day) at ΔP = 0.2 MPa) and a molecular weight cut off at 4.9 × 10⁴ Da. After immersion in mud for 170 days, reduction of R_a was only 8% for UF membrane containing 10 wt% HCEC blend, and was not observed to be obviously different from the membrane containing more than 30 wt% HCEC blend. The higher permeability and rejection of blend membrane may be attributable to the network structure formed via CTA and HCEC penetration.     

A novel neutral polysaccharide having activity on the reticuloendothelial system from the root of Glycyrrhiza uralensis

A neutral polysaccharide, named glycyrrhizan UC, was isolated from the root of Glycyrrhiza uralensis Fischer. It was homogeneous on electrophoresis and gel chromatography, and its molecular mass was estimated to be 69,000. Glycyrrhizan UC is composed of L-arabinose:D-galactose:D-glucose:L-rhamnose in the molar ratio of 10:30 27:1. Methylation analysis, carbon-13 nuclear magnetic resonance and periodate oxidation studies indicated its structural feature as an arabino-3,6-galacto-glucan type polysaccharide.     

Methionine radical cation: structural studies as a function of pH using X- and Q-band time-resolved electron paramagnetic resonance spectroscopy

A comprehensive high resolution electron paramagnetic resonance (EPR) characterization of the l-methionine radical cation and its N-acetyl derivative in liquid solution at room temperature is presented. The cations were generated photochemically in high yield by excimer laser excitation of a water soluble dye, anthraquinone sulfonate sodium salt, the excited triplet state of which is quenched by electron transfer from the side chain sulfur atom of methionine or N-acetylmethionine. The radicals were detected by continuous wave (CW) time-resolved electron paramagnetic resonance (TREPR) spectroscopy at X-band (9.5 GHz) and Q-band (35 GHz) microwave frequencies. At pH values well below the pK(a) of the protonated amine nitrogen, the cation forms a dimer with another ground-state methionine molecule through a S-S three-electron bond. In basic solution, the lone pair on the nitrogen of the amino acid is available to make an intramolecular S-N three-electron bond with the side chain sulfur atom, leading to a five-membered ring structure for the cation. When the amino acid nitrogen is unsubstituted (methionine itself), rapid deprotonation to an aminyl radical takes place at high pH values. If the nitrogen is substituted (N-acetylmethionine), the cyclic structure is observed within its electron spin relaxation time at about 1 micros. Spectral simulation provides chemical shifts (g-factors) and hyperfine coupling constants for all structures, and isotopic labeling experiments strongly support the assignments.     

PHOTOCHEMISTRY OF ACETYLENIC KETONES IN MICELLAR SOLUTIONS AS STUDIED BY PRODUCT-YIELD-DETECTED ESR AND TRANSIENT ABSORPTION TECHNIQUES

The electron spin resonance (ESR) spectra of the transient radical pairs in the photoreduction of 1,5-diphenyl-1,4-pentadiyn-3-one ( I ) and 1,3-diphenyl-2-propyn-1-one ( II ) in sodium dodecyl sulfate (SDS) micellar solutions have been obtained by using the product-yield-detected ESR (PYESR) technique. The PYESR spectra, detected by tracing the microwave effect on the spin-adduct yield as functions of the magnetic field, show the ESR spectra of the ketyl radical of the ketone and SDS radical as the components of the radical pairs. In addition, the growth and the decay processes of the radical pair were observed through detecting the effect of microwave pulse as functions of the delay period between a laser pulse and the off and on time, respectively, of a microwave pulse. The absorption spectra of transient species have also been obtained by using the laser flash photolysis technique. Through the analysis of these data and molecular orbital calculations, the role of acetylenic groups in the photoreactivity of acetylenic ketones is discussed.     

Asymptotic expansions of the distributions of estimators in canonical correlation analysis under nonnormality

Asymptotic expansions of the distributions of typical estimators in canonical correlation analysis under nonnormality are obtained. The expansions include the Edgeworth expansions up to order O(1/n) for the parameter estimators standardized by the population standard errors, and the corresponding expansion by Hall's method with variable transformation. The expansions for the Studentized estimators are also given using the Cornish-Fisher expansion and Hall's method. The parameter estimators are dealt with in the context of estimation for the covariance structure in canonical correlation analysis. The distributions of the associated statistics (the structure of the canonical variables, the scaled log likelihood ratio and Rozeboom's between-set correlation) are also expanded. The robustness of the normal-theory asymptotic variances of the sample canonical correlations and associated statistics are shown when a latent variable model holds. Simulations are performed to see the accuracy of the asymptotic results in finite samples.