Anionic oligomerization of methacrylonitrile

The anionic oligomerization of methacrylonitrile by alcoholic solutions of sodium alkoxide in dimethyl sulfoxide, methanol and ethanol was studied. The DP of the oligomers was directly proportional to the monomer concentration and inversely proportional to the alcohol concentration, in accordance with the equation DP = K[MAN]/[ROH], K being equal to K_p/K_tr. The value of K in DMSO (with sodium methoxidemethanol) was 2.9 ± 0.2, in methanol was 1.5 ± 0.1, and in ethanol (with sodium ethoxide as initiator) was 1.9 ± 0.1. The physical properties of the oligomers are given.     

Absolute stereochemistry of citrinadins a and B from marine-derived fungus

[Structure: see text]. Citrinadin A (2) is a pentacyclic indolinone alkaloid isolated from the cultured broth of a fungus, Penicillium citrinum, which was separated from a marine red alga. The absolute stereochemistry of the pentacyclic core in 2 and its new congener, citrinadin B (1), was elucidated by analysis of the ROESY spectrum for the chlorohydrin derivative (3) of 1 as well as comparison of the electronic circular dichroism (ECD) spectra for 1 and 2 with those of known spirooxiindole alkaloids. On the other hand, the absolute configuration at C-21 bearing an epoxide ring was assigned as S by comparison of the vibrational circular dichroism (VCD) spectra of 1 with those of model compounds 2S- and 2R-2,3-epoxy-3,3-dimethyl-1-phenylpropan-1-one (4a and 4b, respectively).     

Spectroscopic and excited-state properties of tri-9-anthrylborane I: Solvent polarity effects

Spectroscopic and excited-state properties of tri-9-anthrylborane (TAB), showing unique absorption and fluorescence characteristics originating from p(boron)-pi(anthryl group) orbital interactions, were studied in 12 solvents. Although the absorption maximum energy (nu(a)) of TAB which appeared at around 21 x 10(3) cm(-1) (band I) was almost independent of the solvent polarity parameter, f(X) (f(X) = (D(s) - 1)/(2D(s) + 1) - (n(2) - 1)/(2n(2) + 1) where D(s) and n represent the static dielectric constant and the refractive index of a solvent, respectively), the fluorescence maximum energy (nu(f)) showed a linear correlation with f(X). The f(X) dependence of the value of nu(a) - nu(f) demonstrated that the change in the dipole moment of TAB upon light excitation was approximately 8.0 D, indicating that absorption band I was ascribed to an intramolecular charge-transfer transition in nature. The excited electron of TAB was thus concluded to localize primarily on the p orbital of the boron atom. Furthermore, it was shown that the fluorescence lifetime and quantum yield of TAB varied from 11.8 to 1.1 ns and from 0.41 to 0.02, respectively, with an increase in f(X). The present results indicated that the nonradiative decay rate constant (k(nr)) of TAB was influenced significantly by f(X). Excited-state decay of TAB was understood by intramolecular back-electron (charge) transfer from the p orbital of the boron atom to the pi orbital of the anthryl group, which was discussed in terms of the energy gap dependence of k(nr). Specific solvent interactions of TAB revealed by the present spectroscopic and photophysical studies are also discussed.     

Amphidinolide X,a novel 16-membered macrodiolide from dinoflagellate Amphidinium sp

A novel cytotoxic 16-membered macrodiolide, amphidinolide X (1), has been isolated from a marine dinoflagellate Amphidinium sp. (strain Y-42). The gross structure of 1 was elucidated on the basis of spectroscopic data including one-bond and long-range (13)C-(13)C correlations. The relative and absolute stereochemistries were determined by combined analyses of NOESY data and (1)H-(1)H and (1)H-(13)C coupling constants of 1 and NMR data of the degradation products. Amphidinolide X (1) is the first macrodiolide consisting of polyketide-derived diacid and diol units from natural sources. The biosynthetic origins of 1 were investigated by means of feeding experiments with (13)C-labeled acetates.     

Preparation of light-stable micelles with azo dyes from a nonamphiphilic random block copolymer

Light-stable micelles with azo dyes were prepared by micelle formation of a nonamphiphilic diblock copolymer containing azobenzene and UV absorbent at ca. 1 mol% as the unit ratios. The nonamphiphilic block copolymer consists of two different kinds of random copolymer blocks: poly[4-(phenylazophenoxymethyl)styrene-co-vinylphenol] (P(AS-co-VPh)) and poly[4-(2-hydroxybenzophenoxymethyl)styrene-co-styrene] (P(HBS-co-St)). This random block copolymer, P(AS-co-VPh)-b-P(HBS-co-St) formed the micelles in the presence of 1,4-butanediamine (BDA) through hydrogen bond cross-linking between the VPh units via BDA. The micelles had the azobenzene moieties at the cores and the UV absorbents at the coronas. The micelles showed a small color difference in color fading experiments, in comparison with the unimers and with micelles having no UV absorbent at the coronas. It is significant that the diblock copolymer forms the micelles and has the UV absorbents at the coronas to suppress the color fading. Furthermore, the chain length of ,-diamines had no effect on the hydrodynamic radius of the micelles, but affected the aggregation number and the cmc.     

Oxoaminium salts as initiators for cationic polymerization of vinyl monomers

Oxoaminium salt ( 1 ), derived from 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO, 2 ) by one-electron oxidation, could be an initiator for cationic polymerization of vinyl monomers such as isobutyl vinyl ether (IBVE), 2,3-dihydrofuran, p-methoxystyrene, N-vinyl pyrrolidone, etc., to give the corresponding polymers, when 1 had a low nucleophilic counter anion. Formation of the adducts of 1 and IBVE as well as ¹H-NMR and IR data suggested the formation of polymers containing N? O? C structure as the polymer head group. In the polymerization of IBVE, the effects of solvent and concentration of 1 were little observed, however the polymerization rate was dependent on temperature. Furthermore, the thermal reaction of the polymers obtained, which were regarded as prepolymers for block copolymerization and polymeric initiators for radical polymerization, was studied. For example, poly(2-benzylidene-1,3-dioxane) obtained by the polymerization of 2-benzylidene-1,3-dioxane with oxoaminium hexafluoroantimonate ( 1, X = SbF₆) was employed as an initiator for radical polymerization of MMA to give its block copolymer with PMMA. © 1993 John Wiley & Sons, Inc.     

Structural confirmation of oligosaccharides newly isolated from sugar beet molasses

ABSTRACT: BACKGROUND: Sugar beet molasses is a viscous by-product of the processing of sugar beets into sugar. The molasses is known to contain sucrose and raffinose, a typical trisaccharide, with a well-established structure. Although sugar beet molasses contains various other oligosaccharides as well, the structures of those oligosaccharides have not been examined in detail. The purpose of this study was isolation and structural confirmation of these other oligosaccharides found in sugar beet molasses. RESULTS: Four oligosaccharides were newly isolated from sugar beet molasses using high-performance liquid chromatography (HPLC) and carbon-Celite column chromatography. Structural confirmation of the saccharides was provided by methylation analysis, matrix-assisted laser desorption/ionaization time of flight mass spectrometry (MALDI-TOF-MS), and nuclear magnetic resonance (NMR) measurements. CONCLUSION: The following oligosaccharides were identified in sugar beet molasses: beta-D-galactopyranosyl-(1- > 6)-beta-D-fructofuranosyl-(2 <-> 1)-alpha-D-glucopyranoside (named beta-planteose), alpha-D-galactopyranosyl-(1- > 1)-beta-D-fructofuranosyl-(2 <-> 1)-alpha-D-glucopyranoside (named1-planteose), alpha-D-glucopyranosyl-(1- > 6)-alpha-D-glucopyranosyl-(1 <-> 2)-beta-D-fructofuranoside (theanderose), and beta-D-glucopyranosyl-(1- > 3)-alpha-D-glucopyranosyl-(1 <-> 2)-beta-D-fructofuranoside (laminaribiofructose). 1-planteose and laminaribiofructose were isolated from natural sources for the first time.     

Encapsulation and Enhanced Luminescence Properties of IrIII Complexes within a Hexameric Self‐Assembled Capsule

Encapsulation and luminescence studies of [Ir(ppy)₂(bpy)]Cl (ppy=2‐phenylpyridinate, bpy=2,2′‐bipyridine) within a hexameric resorcinarene capsule are reported. One Ir^III complex cation was encapsulated within the capsule, as demonstrated by NMR and dynamic light scattering (DLS) studies. The emission color of the Ir^III complex was drastically changed from orange to yellow by encapsulation, in contrast with the lack of significant changes in the absorption spectrum. The hexameric capsule effectively hampers the non‐radiative pathway to increase both the luminescence quantum yield and the exited state lifetime. The luminescent properties of the encapsulated Ir^III complex depend on the ratio of Ir^III complex to the resorcinarene monomer as well as the concentration of resorcinarene monomer owing to the reversible process of self‐assembly of the hexameric capsule. Quenching experiments revealed that the Ir^III complex in the capsule was effectively separated from quenchers.     

Ultrasound-assisted ozone bleaching of cotton

In this study, the effects of ultrasound on ozone treatment processes for bleaching cotton fabrics were investigated and compared with the conventional hydrogen peroxide bleaching process (60 °C over 90 min). Two ultrasonic + ozone treatments of cotton fabric samples were carried out: (1) ozone in an ultrasonic homogenizer (UH) and (2) ozone in an ultrasonic bath. Ozone dosages, temperature and time variations were determined with both ozone-ultrasonic bleaching processes. Whiteness, yellowness, weight, tensile strength properties, FTIR (ATR) spectra and visual appearance, via scanning electron microscopy of treated cotton fabrics as well as chemical oxygen demand (COD) of bleaching effluents, were investigated. It was concluded that the ozone + UH process, conducted for 30 min at 30 °C, produced closely equivalent values of cotton fabric whiteness and yellowness to the classic peroxide bleaching process, with slightly less weight loss, dramatically less COD in the process effluent (29 mg/l for ozone-UH vs. 4,316 mg/l for classical peroxide treatment), and without causing any adverse and/or detrimental effects on loss of fabric strength or elongation of the cotton fabrics. The ozone-UH process also leads to time and energy savings with much less environmental impact. Consequently, the combination of ozonation plus UH carried out at 30 °C over 30 min can be used successfully for cotton bleaching instead of the classic hydrogen peroxide bleaching process.