Stimuli responsive poly(1-[11-acryloylundecyl]-3-methyl-imidazolium bromide): dewetting and nanoparticle condensation phenomena

A stimuli-responsive homopolymer poly(ILBr) is fabricated via a "two-phase" atom transfer radical polymerization (ATRP) process, where ILBr stands for the reactive ionic liquid surfactant, 1-[11-acryloylundecyl]-3-methyl-imidazolium bromide. An extraordinarily wide molecular weight distribution (PDI = 6.0) was obtained by introducing the initiator (4-bromomethyl methyl benzoate) in a heterogeneous two-phase process. The molecular weight distribution of poly(ILBr) was characterized by size-exclusion chromatography (SEC). The resulting homopolymer was found to be surface active and stimuli responsive. Poly(ILBr) films coated on quartz exhibit stimuli-responsive dewetting after ion exchange of Br(-) by PF(6)(-). This dewetting phenomenon can be understood in chain segmental terms as a stimuli-induced structural relaxation and appears to be the first such reported stimuli-responsive polymeric dewetting. Titrating aqueous poly(ILBr) with aqueous bis(2-ethylhexyl)sulfosuccinate induces nanophase separation and results in the condensation of nanoparticles 30-60 nm in diameter.     

Supramolecular Assembly and Hybridization in Giant Nanomembranes

We demonstrated recently that large nanomembranes became available from inorganic, organic/inorganic and totally organic precursors. Spin coating of mixtures of acrylate monomers and zirconium butoxide (or tetraethoxysilane), when combined with simultaneous radical polymerization and sol-gel reaction, gave 10–30 nm thick, free-standing nanomembranes composed of metal oxides and crosslinked acrylates as interpenetrating network. This approach was extended to thermosetting resins (epoxy, melamine and phthalic resins), to fabricate robust, free-standing nanomembranes. Mechanical properties of the nanomembranes as measured by the bulge test and by a compression method were comparable to those of the corresponding macroscopic resins. The hybrid nanomembrane was subsequently prepared by supramolecular assembly of the nanofilm with surfactants and lipids. These amphiphiles produced adsorbed monolayers on the nanomembrane and some of the assemblies were stably kept in water.     

Generalized Hamiltonian formalism of (2+1)-dimensional non-linear \sigma-model in polynomial formulation

We investigate the canonical structure of the (2+1)-dimensional non-linear model in a polynomial formulation. A current density defined in the non-linear model is a vector field, which satisfies a formal flatness (or pure gauge) condition. It is the polynomial formulation in which the vector field is regarded as a dynamic variable on which the flatness condition is imposed as a constraint condition by introducing a Lagrange multiplier field. The model so formulated has gauge symmetry under a transformation of the Lagrange multiplier field. We construct the generalized Hamiltonian formalism of the model explicitly by using the Dirac method for constrained systems. We derive three types of the pre-gauge-fixing Hamiltonian systems: In the first system the current algebra is realized as the fundamental Dirac Brackets. The second one manifests the similar canonical structure as the Chern-Simons or BF theories. In the last one there appears an interesting interaction as the dynamic variables are coupled to their conjugate momenta via the covariant derivative. Received: 29 September 1998 / Published online: 14 January 1999     

Eigenschaften von Poly(spiro[2,41hepta-4,6-dien) im festen Zustand

Ohne Zusammenfassung     

Der Gegenionen-Effekt auf den sterischen Verlauf der kationischen Polymerisation von Isobutylvinyl?ther

Ohne Zusammenfassung     

Cyclocondensation of F-2-methyl-2-pentene with activated methylene compounds using ‘freeze-dried’ potassium fluoride

The reactions of $\text{F}$-2-methyl-2-pentene with activated methylene compounds such as acetylacetone, ethyl acetoacetate, benzoylacetonitrile, and benzoylmethyl perfluoroalkyl ketones in the presence of potassium fluoride were carried out. Each reaction proceeded smoothly in acetonitrile at room temperature by using ‘freeze-dried’ potassium fluoride as a condensing agent. Acetylacetone and ethyl acetoacetate gave both divinyl ether and pyran compounds, whereas other activated methylene compounds afforded only pyrans in good yields.     

Studies of polymers from cyclic dienes. V. Cationic polymerization of cyclopentadiene,influence of polymerization conditions on the polymer structure

Cationic polymerization of cyclopentadiene was studied with several Friedel-Crafts catalysts, and the influence of polymerization conditions on the polymer structure was investigated. Polycyclopentadiene contained higher amounts of the 1,2 structure when a stronger catalyst and a more polar solvent were used. This fact is discussed in terms of the tightness of the growing ion pair. The polymer structure did not vary with polymerization temperature in toluene solvent. In methylene chloride at around 0°C. the structural variation with catalysts was much smaller, suggesting a freer nature of the growing ion pair. The viscosity data also support the change in the structure of the ion pair under similar conditions. The use of aliphatic hydrocarbon solvents gave the highest contents of the 1,2 structure. This results was ascribed to the lack of solvation, considering the dependence of the polymer structure on the monomer concentration, which was found only in this solvent. Furthermore, isomerization during propagation was observed in polar solvents at higher temperature.     

Carbocyclization by homolytic substitution (SH′ process). A new route to dihydroindole or dihydrobenzofuran

N-(4-Phenylthio-2-butenyl)-2-bromoaniline reacted with tributyltin hydride to give 3-vinyl-2,3-dihydroindole in 96% yield via hitherto unknown intramolecular S_H′ process, some other examples and remarkable dilution effect on these homolytic carbocyclizations were described.     

Palladium-catalyzed asymmetric allylic substitution of 2-arylcyclohexenol derivatives: asymmetric total syntheses of (+)-crinamine, (-)-haemanthidine, and (+)-pretazettine

Much interest has been shown in Amaryllidaceae alkaloids as synthetic targets due to their wide range of biological activities. Over 100 alkaloids have been isolated from members of the Amaryllidaceae family; most of them can be classified into eight skeletally homogeneous groups. We have succeeded in the first asymmetric total syntheses of the crinane-type alkaloids (+)-crinamine (1), (-)-haemanthidine (2), and (+)-pretazettine (3). The starting cyclohexenylamine 14 was obtained from allyl phosphonate 11c by palladium-catalyzed asymmetric amination in 82% yield and with 74% ee. The product was recrystallized from MeOH. Interestingly, (-)-14 with 99% ee was obtained from the mother liquor (74% recovery). Intramolecular carbonyl-ene reaction of (-)-10 proceeds in a highly stereoselective manner to give hexahydroindole derivative 9 as the sole product. In the Lewis-acid-catalyzed carbonyl-ene reaction, an interesting rearrangement product, 20, was isolated in high yield. From 9, (+)-crinamine was synthesized. Thus, the asymmetric total synthesis of (+)-crinamine was achieved in 10 steps from 11c, and the overall yield is 19%. The total synthesis of (-)-haemanthidine was also achieved from 9 by a short sequence of steps.     

Studies on polymers from cyclic dienes. XII. Cationic polymerization of spiro[2,4]hepta-4,6-diene

Polymerizations of spiro[2,4]hepta-4,6-diene were carried out with cationic initiators and Ziegler-type catalysts. This monomer polymerized very rapidly with a variety of cationic initiators, and low monomer and initiator concentrations had to be employed in order to avoid formation of crosslinked polymers. The polymer contained 1,2 and 1,4 addition units, and there was no indication of the opening of the cyclopropyl ring in the monomer unit. The following relationship was obtained: [η] = 4.5 × 10^?8M?_n^1.71. The exponential coefficient of this equation is much greater than those typical of vinyl polymers, suggesting that the polymer chain is very stiff. The polymer showed much enhanced resistance to autoxidation as compared with polycyclopentadiene, and its softening point was above 200°C. These interesting physical and chemical properties of the monomer and the polymer can be associated with their spiro structures.