A new nonpeptide tachykinin NK1 receptor antagonist isolated from the plants of Compositae

To find new tachykinin NK1 receptor antagonists from natural sources, we examined the tachykinin antagonist activity in the extracts of approximately 200 species of plants by the use of isolated guinea pig ileum. As a result, we discovered a novel and potent NK1 receptor antagonist in the extract of dried flowers of Matricaria chamomilla L. (chamomile). The structure of the antagonist was established as N1,N5,N10,N14-tetrakis[3-(4-hydroxyphenyl)-2-propenoyl]-1,5,10,14-tetraazatetradecane (tetracoumaroyl spermine, 1a). The Ki values of 1a, estimated from the inhibitory action on the substance P (SP)-induced contraction of the guinea pig ileum and the inhibition of the binding of [3H][Sar9, Met(O2)11]SP to human NK1 receptors, were 21.9 nM and 3.3 nM, respectively. 1a is the first potent NK1 receptor antagonist from natural sources and it has a unique structure of a polyacylated spermine. 1a was concentrated in pollen of Matricaria chamomilla L. and was also found in the extracts of flowers of other four species of Compositae. In addition, we found N1,N5,N10-tris[3-(4-hydroxyphenyl)-2-propenoyl]-1,5,10,14-tetraazatetradecane (2) as a new compound in the extract of flowers of Matricaria chamomilla L., which did not exhibit any tachykinin antagonist activity. A number of related compounds were synthesized, and the structure-activity relationship was studied.     

Preparation and evaluation of solid dispersion for nitrendipine-carbopol and nitrendipine-HPMCP systems using a twin screw extruder

In the present study, we prepared solid dispersions of the poorly water-soluble drug nitrendipine (NIT) using the twin screw extruder method with high-molecular-weight substances, hydroxypropylmethylcellulosephthalate (HPMCP) and Carbopol (CAR), as carriers. Powder X-ray diffraction (PXRD) and differential scanning calorimetry (DSC) evaluation showed that solid dispersions can be formed when NIT-HPMCP and NIT-CAR mixtures are treated with the twin screw extruder method. Fourier Transformation IR Spectroscopy (FT-IR) obtained with NIT-HPMCP and NIT-CAR solid dispersions indicated the presence of hydrogen bonding between the drug and the carriers. NIT-CAR solid dispersions were found to give somewhat higher dissolution than crystalline NIT and physical mixtures, while the dissolution of NIT-HPMCP solid dispersions was markedly decreased compared with the crystalline NIT and physical mixtures. These findings indicated that CAR has a greater ability to improve the dissolution of NIT than HPMCP when a twin screw extruder was employed to prepare the solid dispersions. The twin screw extruder method can be used as a simple and effective method for the preparation of solid dispersions to improve the dissolution properties of poorly water-soluble drugs when choosing proper polymers as carriers.     

An analysis of regional ventilation in pulmonary sarcoidosis by inspired 133Xe washout test

Xenon-133 ventilation study were used to measure regional ventilation in seven patients with pulmonary sarcoidosis and in four normal subjects. For the purpose of analyzing the washout curves on the whole lungs, two ventilation indexes were calculated, which were TA/H and T1/2. TA/H is that the area under the curve divided by the difference in mean count rate during equilibrium and at 120 s after washout started. T1/2 value represents the time required to 50% of the mean count rate during equilibrium. The average time of TA/H on the whole lung was 13.5 +/- 1.1 s in normal subjects (n = 4), 13.0 +/- 4.3 s in stage I (bilateral hilar lymphadenopathy without lung involvement on chest X-ray) sarcoidosis (n = 3), 21.3 +/- 1.8 s in stages I, II (lung involvement) sarcoidosis (n = 4). The average time of T1/2 on the whole lung was 43.7 +/- 4.7 s in normal subjects, 42.3 +/- 16.0 s in stagel sarcoidosis, 72.5 +/- 28.6 s stages II, III sarcoidosis. The ventilation indexes on the regional lungs showed almost a similar tendency to that on the whole lung. The ventilation indexes in patients with stage II, III sarcoidosis were significantly longer than in normal subjects and in patients with stage I sarcoidosis. It was suggested that 133Xe washout test might detect regional ventilation abnormalities which were not recognized on chest X-ray in pulmonary sarcoidosis.     

Iridium-catalyzed hydroboration of alkenes with pinacolborane

Hydroboration of terminal and internal alkenes with pinacolborane (1.2 equiv) was carried out at room temperature in the presence of an iridium(I) catalyst (3 mol%). Addition of dppm (2 equiv) to [Ir(cod)Cl]₂ gave the best catalyst for hydroboration of aliphatic terminal and internal alkenes at room temperature, resulting in addition of the boron atom to the terminal carbon of 1-alkenes with more than 99% selectivities. On the other hand, a complex prepared from dppe (2 equiv) and [Ir(cod)Cl]₂ resulted in the best yields for vinylarenes such as styrene. These complexes exhibited higher levels of catalyst activity and selectivity than those of corresponding rhodium complexes.     

Red luminescence in MgO-GeO<Subscript>2</Subscript> gel glasses and glass ceramics doped with Mn ions prepared by sol-gel method

To obtain red luminants, MgO-GeO₂ gel glasses and glass ceramics doped with manganese ions were prepared by a sol-gel method and their properties were investigated by measuring X-ray diffraction (XRD), electron spin resonance (ESR), and luminescence and excitation spectra. Under UV irradiation at 254 nm, the gel glasses and glass ceramics showed red luminescence at 620–665 nm, the intensity of which became strong with increasing the heat-treatment temperature. A glass ceramic with the composition 1.0MnO-25MgO-75GeO₂ heat treated at 1000°C exhibited the strongest red luminescence at 661 nm. From the results of XRD and ESR, this luminescence is found to be due to the transition from the ⁴T_1g to the ⁶A_1g state of octahedrally coordinated Mn²⁺ ions located in MgGeO₃ polycrystals. The luminescence wavelength of the glass ceramics (∼665 nm) is long compared with Eu³⁺-containing phosphors (612 nm), therefore the glass ceramics can be expected for red luminants.     

Direct and sensitized photodecompositions of 1-phenyldiazoethane : The spin state in the 1,2-hydrogen migration to the carbene center

Direct and sensitised photodecompositions of 1-phenyl-diazoethane (2) were investigated in cis and trans-2-butenes, and also in ethyl ether. In cis-2-butene photosensitisation led to the increased formation of acetophenone (5) and to loss of stereospecificity of the addition reaction. In ethyl ether an increased yield of 5 was obtained. On the other hand, the yield of styrene (4), which was produced via 1,2-hydrogen migration, decreased with sensitisation. These results indicate that the spin state in the 1,2-hydrogen migration to the divalent carbon is singlet.     

Surface grafting of polyethylene by mutual irradiation in methyl acrylate vapor. I. γ irradiation

Mutual irradiation of polyethylene (PE) in methyl acrylate vapor easily forms a poly(methyl acrylate) (PMA) homopolymer layer on the inner graft copolymer layer consisting of both PE and PMA components as a result of the rapidly increasing surface-graft composition. This growth process of surface grafting has been found to provide some specific kinetic features different from those in other surface-grafting systems. With formation of the surface homopolymer layer, low- and highdensity PE sheets give the same grafting rate, whereas both sheets give different rates in grafting stages or conditions in which the homopolymer layer is not formed. This result indicates that most monomers, penetrating across the surface, are entrapped or consumed in the surface homopolymer layer; accordingly the rate becomes independent of the type of PE sheets that have significantly different diffusion coefficients. The thickness of the inner graft copolymer layer, which is kept constant after homopolymer-layer formation, increases with decreasing dose rate and with increasing monomer vapor pressure and temperature. This behavior can be qualitatively explained according to an equation for the initial steady-state grafting depth.     

Selective Ni-P electroless plating on photopatterned cationic adsorption films influenced by alkyl chain lengths of polyelectrolyte adsorbates and additive surfactants

We demonstrated that the photopatterned single-layer adsorption film of poly(1-dodecyl-4-pyridinium bromide) on a silica surface was available for a template of nickel-phosphorus (Ni-P) electroless plating through sensitization with a SnCl(2) aqueous solution and activation with a PdCl(2) aqueous solution. Four kinds of poly(1-alkyl-4-vinylpyridinium halide)s bearing methyl, propyl, hexyl, and dodecyl groups were prepared. The cationic polymers were adsorbed by a negatively charged silica surface from their solutions, to form single-layer adsorption films exhibiting desorption-resistance toward deionized water and ethanol. The organic adsorption films could be decomposed completely by exposure to 172 nm deep-UV light. The formation and decomposition of the single-layer films were confirmed by deep-UV absorption spectral measurement and zeta-potential measurement. Ni-P electroless plating was carried out on the photopatterned adsorption films, using three types of SnO(x) colloidal materials without and with cationic or anionic surfactant as catalyst precursors in the sensitization step. In the case of the negatively charged SnO(x) colloids surrounded by anionic surfactant, Ni-deposition took place preferentially on the cationic adsorption films remaining in unexposed regions. The Ni-deposition was accelerated significantly on the cationic adsorption film bearing dodecyl groups. It was obvious by ICP-AES analyses that the hydrophobic long-chain dodecyl groups in the adsorption film could promote the adsorption of the negative SnO(x) colloids on the film surface, followed by much nucleus formation of zerovalent Pd catalysts useful for the electroless plating. The result of our experiment clearly showed that, in addition to electrostatic interaction, van der Waals interaction generating between the hydrophobic long-chain hydrocarbons of the adsorption film and the surfactant improved significantly the adsorption stability of the SnO(x) colloids, resulting in highly selective Ni-deposition in accord with the photopattern shape of the cationic single-layer adsorption film.     

ACTION SPECTRA FOR LIGHT-INDUCED DE-EPOXIDATION AND EPOXIDATION OF XANTHOPHYLLS IN SPINACH LEAF*

Abstract— The action spectra for violaxanthin de-epoxidation and zeaxanthin epoxidation in New Zealand spinach leaf segments, Tetragonia expansa, were determined at equal incident quanta of 2·0 × 10¹⁵ quanta cm^-2 sec^-1. Precise action spectra were not obtained due to variable leaf activity. The de-epoxidation action spectrum had major peaks at approximately 480 and 648 nm. Blue light was slightly more effective than red light and little activity was observed beyond 700 nm. The epoxidation action spectrum showed major peaks at around 440 and 670 nm. Blue light was more effective than red light and light beyond 700 nm showed definite activity. The net result of de-epoxidation and epoxidation is a cyclic scheme, the violaxanthin cycle, which consumes O₂ and photoproducts. The action spectra indicate that the violaxanthin cycle is more active in blue than in red light and therefore could account for O₂ uptake stimulated by blue light. However, the violaxanthin cycle is not the pathway for O₂ uptake by photosynthetic system 1. It was suggested that the violaxanthin cycle may function as a pathway for the consumption of excess photoproducts generated in blue light or the conversion of these photo-products to other forms of energy.     

Enzymic method for the spectrophotometric determination of aspartame in beverages

A sensitive spectrophotometric method for the determination of aspartame in beverages is described. The method involves the enzymic conversion of aspartame into formaldehyde by the alpha-chymotrypsin-alcohol oxidase system, followed by the formation of a chromophore with 4-aminopent-3-en-2-one. The calibration graph was linear in the range 2.0-30.0 micrograms ml-1 of aspartame. Many common ingredients of beverages do not interfere with the proposed method. The method was applied to the determination of the aspartame content of various real samples, and the results obtained were compared with those given by high-performance liquid chromatography.