Ultrafast single‐electron‐transfer/degenerative‐chain‐transfer mediated living radical polymerization of acrylates initiated with iodoform in water at room temperature and catalyzed by sodium dithionite

Sodium dithionite in the presence of NaHCO₃ in water acts as a single‐electron‐transfer agent and facilitates the single‐electron‐transfer/degenerative‐chain‐transfer mediated living radical polymerization (SET–DTLRP) of acrylates initiated with iodoform at room temperature. The resulting α,ω‐di(iodo)polyacrylates can be used as macroinitiators for the SET–DTLRP of other acrylates. Ultrahigh‐molar‐mass poly(tert‐butyl acrylate) can be synthesized via the SET–DTLRP of tert‐butyl acrylate and has a very low weight‐average molecular weight/number‐average molecular weight ratio of 1.15. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2178–2184, 2005     

Carbon-13 nuclear magnetic resonance spectra of potent antimalarials: Primaquine and chloroquine

C¹³ Nmr chemical shits of primaquine and chloroquine are reported. The signals are assigned on the basis of substituent effects on benzene shifts, intensities, multiplicities in SFORI) and the comparison with structurally related compounds.     

Experimental limits on the mass and decay lifetime of νμ

The nonobservation of photon-induced e⁺e^? pairs pointing in the neutrino beam direction in large bubble chambers would allow one to set an upper limit on the product m_νμλ^CM for muon-type neutrinos, where m_νμ is the mass and λ^CM is the intrinsic partial decay width in sec^?1 for ν_μ→γ+X. In the theory of Eliezer and Ross where , this implies an upper limit on m_νμ considerably smaller than the present upper limit, and a large lower limit on the lifetime τ_νμ.     

Fourier transform 13C NMR analysis of benzodiazepines

The natural abundance carbon-13 nuclear magnetic resonance spectra of diazepam, clonazepam, flurazepam and chlordiazepoxide were recorded in suitable solvent using the Fourier transform technique on a JEOL FX-60 spectrometer. The relaxation time (T₁) of these compounds were also measured. The chemical shift of the various carbon resonances have been assigned on the basis of chemical shift theory, multiplicity generated in single-frequency off-resonance decoupled spectra, relaxation time and the chemical shifts of the model compounds.     

Light scattering from a nematic monodomain in an electric field Twist elastic constant and viscosity coefficient of nematic polymer–solvent mixtures

Abstract

The light scattering technique was used to investigate the viscoelastic parameters characterizing director twist distortions in miscible nematic mixtures of 5CB (pentacyanobiphenyl) with two side chain liquid crystal polymers and a main chain liquid crystal polymer. By applying an AC electric field to homeotropically-aligned nematic monodomains of the mixtures, the field-dependent scattering intensities and director orientation fluctuation relaxation rates yield, respectively, the twist elastic constant K ₂₂ and viscosity coefficient γ₁. The results directly demonstrate that the addition of liquid crystal polymers causes substantial decreases of the relaxation rates for dynamic light scattering from the twist mode and these changes are due to small decreases in K ₂₂ coupled with large increases in γ₁. The decrements in K ₂₂ are comparable for both side chain and main chain liquid crystal polymers. The relative increase in the twist viscosity for the side chain liquid crystal polymers is much smaller than those of main chain polymers. A theoretical model is used to qualitatively interpret the difference between the viscous behaviour of the twist mode for both side chain and main chain liquid crystal polymers in a nematic solvent.     

Isomorphism within the hexagonal columnar mesophase of molecular and macromolecular self- and co-assembled columns containing tapered groups

Abstract

The phase behaviour of binary mixtures of self-assembled tapering molecules based on monoesters of oligooxyethylene glycol and 3,4,5-tris[4-(n-dodecan-1-yloxy)benzyloxy]benzoic acid, their corresponding polymethacrylates, and of 4′-methyl (benzo-15-crown-5)-3,4,5-tris[4-(n-dodecan-1-yloxy)benzyloxy]benzoate within their hexagonal columnar mesophase (Φ_h) is described. The binary blends between molecular tapers co-assemble into a single supramolecular column resulting in isomorphism within their Φ_h mesophase over the entire range of composition. The binary blends between polymethacrylates containing tapered side groups co-assemble into a single Φ_h phase only when the columns of the parent polymers are of similar diameters. This results in binary mixtures which are isomorphic within the Φ_h mesophase over the entire composition range. When the diameters of the columns formed by the parent polymers are dissimilar, isomorphic mixtures are obtained only over a narrow range of composition. Binary mixtures between molecular tapers and macromolecular systems containing tapered side groups co-assemble into a single column to the extent that intercalation of the molecular taper, within the column formed by the macromolecular system containing tapered side groups, is permissible. In all systems increased intracolumnar interactions can be induced by complexation of CF₃SO₃Li by the oligooxyethylenic receptors leading to isomorphism in otherwise non-isomorphic mixtures. Ternary mixtures between molecular tapers with non-specific oligooxyethylenic receptors and specific crown ether receptors and CF₃SO₃ Na as the third component are non-isomorphic within their Φ_h phase due to preferential complexation of the alkali metal cation by the column of the crown ether containing the molecular taper. This results in two columns of dissimilar diameters, which are isomorphic in the Φ_h phase only within a limited range of composition.     

Phenylacetylene-Methyl Acrylate Radical Copolymers

Abstract

Phenylacetylene (PA, M₂) and methyl acrylate (Mi) copolymerization can be described by the simple terminal model having the parameters r₁ = 0.67 and r₂ = 0.11. ¹H-NMR spectroscopy shows the predominant trans configuration of PA units, the high tendency of coisotactic alternating addition, and influence of temperature on the chain conformation.