Synthesis of bioactive indolocarbazoles: synthesis, nucleophilic ring-opening and chiral base desymmetrisation of a cyclic sulfate intermediate

A number of new functionalised bridged indolocarbazole systems have been prepared by ring-opening reactions of a key cyclic sulfate intermediate, prepared from the corresponding diol by the action of sulfuryl diimidazole and DBU. The same cyclic sulfate also undergoes an unprecedented asymmetric rearrangement to a chiral ketone, on treatment with a chiral lithium amide base.     

Photorefractive Four-Wave Mixing Switches Utilizing Pockels Effect -Longitudinal and Lateral Switches-

We carried out detailed calculations for photorefractive wave-mixing switches based on one of three crystals with high electro-optic coefficients, namely, BaTiO₃, Strontium Barium Niobate (SBN (0.75)), and Potasium Sodium Strontium Barium Niobate (KNSBN). A comparison of results for the three crystals shows that a 0_-cut BaTiO³ crystal is suitable for a longitudinal switch and requires a voltage of about 80 for a 2-mm-thick crystal to induce sufficient phase mismatch. The electrodes must be transparent for the incident and diffracted beams. A 45_-cut SBN (0.75) crystal, however, is suitable for a lateral switch and requires a voltage of about 150 for a 1-mm-wide crystal. The electrodes do not need to be transparent.     

Light Diffraction of Aligned Polymer Fibers Periodically Dispersed by Phase Separation of Liquid Crystal and Polymer

We have confirmed light diffraction of aligned polymer fibers obtained by a phase separation of an anisotropic-phase solution of liquid crystal and polymer. He—Ne laser light passing through the polymer fibers was scattered in the axis vertical to the fibers, and had two peaks of light intensity symmetrical to the center of the transmitting laser spot. The two peaks were found to be caused by light diffraction due to the periodic polymer-fiber dispersion because the peaks corresponded to values calculated by intervals between the fibers. The periodical fiber networks are considered to be formed by anisotropic spinodal decomposition. This effect can be used to measure the dispersion order of the polymer fibers. © 2004 The Optical Society of Japan     

Measurements of Time-Varying Characteristics of Optical Signals and Inhomogeneities of Tested Substances with Additional Phase Modulation

The problem of investigation of the amplitude and phase structure of a time-varying probing optical signal and the structure of time-varying inhomogeneities of a substance tested by this signal is considered. The analysis is concerned, in particular, with determination of the structure of signals and processes with resolution in the pico- and femtosecond range. The scheme used for the analysis is based on registration of four spatially separated spectra of the studied radiation. The spectra are formed in a four-channel scheme with a twin-wave Michelson interferometer and a spectral device. Modulators based on electrooptical crystals (perovskites) are placed in the channels. The sum spectra are formed: without modulators, with the effect of either of the modulators, and with both of them affecting the radiation. The effect of the studied substance implies either modulating the radiation (in this case it is described by multiplication) or redistributing the radiation (then it is described by convolution).     

New liquid‐crystalline poly(ester amide)s: The role of nitro groups in the phase behavior

New hydrogen‐bonded liquid‐crystalline poly(ester amide)s (PEA)s were obtained from 1,4‐terephthaloyl[bis‐(3‐nitro‐N‐anthranilic acid)] (5) or 1,4‐terephthaloyl[bis‐(N‐anthranilic acid)] (6), with or without nitro groups, respectively, through the separate condensation of each with hydroquinone or dihydroxynaphthalene. The dicarboxylic monomers were synthesized from 2‐aminobenzoic acid. The phase behavior of the monomers and polymers were studied with differential scanning calorimetry, polarized light microscopy, and wide‐angle X‐ray diffraction methods. Monomer 5, containing nitro groups, exhibited a smectic liquid‐crystalline phase, whereas the texture of monomer 6 without nitro groups appeared to be nematic. The PEAs containing nitro groups exhibited polymorphism (smectic and nematic), whereas those without nitro groups exhibited only one phase transition (a nematic threaded texture). The changes occurring in the phase behavior of the polymers were explained by the introduction of nitro groups. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1289–1298, 2004     

Shear banding in strained semicrystalline polyamide 6 films as revealed by atomic force microscopy: Role of the amorphous phase

Atomic force microscopy (AFM) has been used to visualize the plastic deformation mechanisms that are responsible for the yielding of semicrystalline polymers of low degree of crystallinity (<50%). Indeed, AFM, if operated in suitable conditions, is able to image both the amorphous and the crystalline phases. Polyamide 6 films have been drawn at temperatures T < 160 °C. Postmortem AFM observations show that, at yield, shear bands nucleate and propagate in the amorphous phase. They cross the crystalline lamellae and run over the whole surface of the sample. By crossing the lamellae, they form nanoblocks of uniform size. Neither the size of the nanoblocks nor the angle between the tensile axis and the shear bands can be explained in terms of crystal plasticity. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 687–701, 2004     

The effect of compatibilization and rheological properties of polystyrene and poly(dimethylsiloxane) on phase structure of polystyrene/poly(dimethylsiloxane) blends

The compatibilization effect of polystyrene (PS)‐poly(dimethylsiloxane) (PDMS) diblock copolymer (PS‐b‐PDMS) and the effect of rheological properties of PS and PDMS on phase structure of PS/PDMS blends were investigated using a selective extraction technique and scanning electron microscopy (SEM). The dual‐phase continuity of PS/PDMS blends takes place in a wide composition range. The formation and the onset of a cocontinuous phase structure largely depend on blend composition, viscosity ratio of the constituent components, and addition of diblock copolymers. The width of the concentration region of the cocontinuous structure is narrowed with increasing the viscosity ratio of the blends and in the presence of the small amount diblock copolymers. Quiescent annealing shifts the onset values of continuity. The experimental results are compared with the volume fraction of phase inversion calculated with various theoretical models, but none of the models can account quantitatively for the observed data. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 898–913, 2004     

The interaction between poly(N-isopropylacrylamide) and salts in aqueous media: The “salting-out” phenomenon as studied by attenuated total reflection/fourier transform infrared spectroscopy

The effect of two strong salting-out salts (Na₂SO₄ and K₂SO₄) on the temperature-induced phase-separation process in aqueous solutions of poly(N-isopropylacrylamide) (PNIPA) was examined by attenuated total reflectance/Fourier transform infrared spectroscopy, differential scanning calorimetry, and viscosity measurements. On the basis of these measurements, a detailed scenario of the phase-separation process was deduced. The phase-separation scenario of solutions containing PNIPA and water was altered in the presence of sulfate ions. Here, the sulfate ions induced partial intrachain collapse, manifested by a relatively compact structure well below the lower critical solution temperature. This led to a more gradual, smooth phase transition, with temperature-resolved intrachain collapse and interchain aggregation and a lesser extent of hysteresis. Although at the macrolevel one may not be able to differentiate among various scenarios altering the solvent into a poor solvent, the aforementioned microlevel measurements provided a way to expose the difference between raising the temperature and adding cosolutes. Follow-up studies on the effect of salting-in salts will be presented. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 33–46, 2004     

Solid Phase Synthesis of 2-Substituted 1,3-Oxazin-6-ones Using Resin-bound Cyclic Malonic Acid Ester

A facile solid phase synthesis of 2-substituted 1,3-oxazin-6-ones using polymer-supported Meldrum‘s acid has been reported. Reaction of the resin-bound cyclic malonic acid ester with triethyl orthoformate and subsequent double substitution with amide, afforded the corresponding polymer-supported acylaminomethylene cyclic malonic acid ester, which upon thermal treatment led to 1, 3-oxazin-6-ones in good yields and with high purity.