Radiation-induced copolymerizations of perfluorovinyl acetic acid and its methyl ester with α-olefin

Homopolymerizations and copolymerizations of perfluorovinyl acetic acid (FVA) and its methyl ester (MFVA) were carried out by γ radiation at a temperature of 25°C, a dose rate of 1 × 10⁶ rad/hr, and FVA/α-olefin and MFVA/α-olefin ratios of 10/90-90/10 in the monomer mixture. FVA and MFVA gave small quantities of brown and greasy low-molecular-weight homopolymers. The polymerization rates of both FVA and MFVA were extremely small, as shown by the maximum G value of monomer consumption of 12. FVA and MFVA reacted with α-olefin to form waxlike copolymers. The copolymerization rates of both FVA and MFVA with α-olefin were remarkably larger than those of the homopolymerizations, particularly with ethylene. The polymer compositions of FVA/ethylene or MFVA/ethylene was nearly 1/2 over a wide range of the monomer compositions. The Mayo–Lewis method gave negative r₁ (FVA) and r₁ (MFVA). The polymer composition curves could be well interpreted by introducing the penultimate model.     

Resonance Raman scattering with a forbidden but vibronically allowed electronic transition: Excitation profiles of combinations and overtones of copper tetraphenylporphyrin in the Q-band resonance

Resonance Raman scattering with the Q band of CuTPP shows a peculiar intensity pattern; bands due to combinations and overtones are strong, whereas the corresponding fundamentals are very weak. By a quantitative analysis of excitation profiles, this phenomenon has been fully accounted for on the basis of the vibronic theory of Raman intensities. Vibronic coupling parameters between the Q and B states of CuTPP have been obtained.     

Copper-catalyzed allylation of carbonyl derivatives using allyl(2-pyridyl)silanes

[reaction: see text] We have developed an efficient copper-catalyzed allylation of carbonyl derivatives using allyl(2-pyridyl)silanes, in which the strong directing effect of the 2-pyridyl group was observed. A useful synthesis and allylation of substituted allyl(2-pyridyl)silanes is also described.     

Coumarin-conjugated cyclodextrins: remarkable enhancement of the chemical-to-light energy transfer efficiency

One or two coumarin units were incorporated to the primary face of γ-cyclodextrin (γ-CD), and the resultant coumarin derivatives were employed to harvest the chemical energy generated in the reaction of bis(trichlorophenyl)oxalate with hydrogen peroxide. In comparison with the coumarin without CD cavity for molecular recognition, the coumarin–CD conjugates demonstrated much higher chemiluminescence inetensity, indicating that the CD moiety remarkably improves the chemical energy transfer.     

Metal-metal d-d interaction through the discrete stacking of mononuclear M(II) complexes (M = Pt, Pd, and Cu) within an organic-pillared coordination cage

Two molecules of planar MII(acac)2 complexes (M = Pt, Pd, and, Cu; acac = acetylacetonato) are efficiently stacked within an organic-pillared coordination cage, exhibiting characteristic spectroscopies (for M = Pt and Pd) and electron spin-spin coupling (for M = Cu) attributable to metal-metal interaction.     

Polymeric organosilicon systems. XVII. Synthesis and photochemical and conducting properties of poly[o-and m-(disilanylene)phenylene]s

Poly[o-(tetramethyldisilanylene)phenylene] ( 2a ), poly[o-(1,2-dimethyldiphenyldisilanylene)-phenylene] ( 2b ), poly[m-(tetramethyldisilanylene)phenylene] ( 2c ), and poly[m-(1,2-dimethyldiphenyldisilanylene)phenylene] ( 2d ) were prepared by the sodium condensation reaction of the corresponding 1,2-and 1,3-bis (chlorosilyl)benzenes in toluene. Irradiation of thin films of 2a-2d in air resulted in a rapid decrease of absorption maxima in the ultraviolet region. The photolysis of 2b and 2d in benzene afforded photodegradation products with low molecular weights. When thin films of 2b and 2d were doped with antimony pentafluoride vapor, films which have conductivities of semi-conductor level were obtained. © 1993 John Wiley & Sons, Inc.     

Structural assignment of n3-acylated uridine derivatives by means of 13c nmr spectroscopy

Diisopropylethylamine was effective as a base for acylation of 2′,3′,5′-tri-O-acetyluridine with various acid chlorides. The ¹³C NMR spectra of the products and related compounds showed clearly that the acyl groups intoduced to the uracil moiety are attached to the N³-nitrogen.     

exo- and enantioselective cycloaddition of azomethine ylides generated from N-alkylidene glycine esters using chiral phosphine-copper complexes

High diastereo- and enantioselectivities were obtained for the asymmetric 1,3-dipolar cycloaddition of azomethine ylides generated from N-alkylideneglycine esters with dipolarophiles using chiral phosphine-copper complexes as catalysts. Whereas the cycloaddition of azomethine ylides catalyzed by metal salts generally afforded endo-adducts as the predominant product, the present method is the first example of an exo-selective cycloaddition. [reaction: see text]     

Cp/mas 13c nmr and Electron Diffraction Study of Bacterial Cellulose Structure Affected by Cell Wall Polysaccharides

Acetobacter xylinum was cultured in Schramm–Hestrin medium containing pectin (pectin medium), xylan (xylan medium), or glucomannan (mannan medium). X-ray diffractometry revealed that xylan and glucomannan affected the size of the cellulose crystals and their d-spacing values. Solid-state cross polarization magic angle spinning carbon-13 nuclear magnetic resonance spectroscopy indicated that the ratio of cellulose I was reduced by the addition of polysaccharides. These effects were more remarkable on the cellulose in the mannan medium than that in the xylan medium, and were scarcely observed in the pectin medium. Electron diffraction analysis revealed that these effects on hemicelluloses along cellulose microfibrils are continuous in the mannan medium and discontinuous in the xylan medium. These findings suggest that the uronic acid in the polysaccharides prevents interactions with cellulose leading to alterations of the structure of the cellulose crystal.