Enantiomer separation by reversed-phase liquid chromatography with novel hydrophobic phases composed of chiral cationic surfactants

This paper describes enantiomer separation using four kinds of chiral stationary phases (CSPs) where quaternary ammonium surfactants containing L-valine diamide moieties into long alkyl chains were bound to silicagel supports by reversed phase liquid chromatography. Our aim was to examine hydrogen bonding association of the chiral moiety in hydrophobic phase brought about by aggregation of the micelle-forming surfactants on the surface. The following CSPs were thus derived from the vinyl-terminated chiral surfactants via hydrosilylation: CSP 1 from N-[3-(10-undecenoyl-L-valylamino)propyl]-N,N,N-trimethylammonium bromide, CSP 2 from N-[6-(10-undecenoyl-L-valylamino)hexyl]-N,N,N-trimethyl-ammonium bromide, CSP 3 from N-[3-(10-undecenoyl-L-valylamino)propyl]-N-octadecanyl-N,N-dimethyl-ammonium bromide and CSP 4 from N-[6-(10-undecenoyl-L-valylamino)hexyl]-N-octadecanyl-N,N-dimethylammonium bromide. The degree of hydrophobicity in the interfacial phase was observed by measuring pyrene fluorescence in aqueous media including an organic modifier. Retention of racemic N-acylleucine isopropyl esters was highest in CSP 4, followed by 3, 2, and 1. Largest alpha values toward enantiomer separation were observed for CSP 4 where the chiral moieties were kept through a hexamethylene unit apart from the polar head groups and to which another long alkyl chain was attached, as compared with those for CSP 4. In CSP 4, the chiral moiety to interact with enantiomeric solutes should be buried into the interfacial phase deeply in more extent than CSP 3. In a similar manner, CSP 2 has more effective for enantiomer separation than CSP 1. The interfacial phase of these CSPs was easily exposed to the bulk phase because of the affinity between the bulk phase and the polar head groups as well as their electrostatic repulsion. However, degree of the enantiomer separation can be controlled by the depth of the chiral moiety in the hydrophobic interfacial phase.     

Liquid crystalline gel beads of curdlan

Curdlan beads consisting of liquid crystalline gel (LCG) and amorphous gel (AG) in alternating layers in a wide range of diameters were newly prepared by interfacial insolubilization reactions using calcium chloride as the setting reagent. The thickness of the liquid crystalline layer was proportional to the diameter of the gel bead, and the proportional constant agreed with that determined for the cylindrical gel prepared by a dialysis method. The proportional constant initially increased with increasing calcium concentration of the dispersing medium and saturated at a high concentration limit. These results suggest that the mechanisms for forming the alternating LCG/AG structures prepared with different boundary conditions are the same. The LCG/AG structure could be controlled by calcium concentration.     

Molecular weight distribution and molecular structure of polyethylene produced by radiation-induced polymerization

The molecular weight distribution of polyethylene produced by radiation was calculated according to a kinetic scheme. The calculated molecular weight distribution was compared with the results deduced from gel-permeation chromatography. The observed distribution curve from GPC was broader and showed a lower degree of polymerization than the calculated one. Discrepancies between observed and calculated curves can be explained if the polymer contains nonsteady-state products and if the reaction mechanism includes chain transfer to dead polymer. By this reaction long-chain branching would occur. Several long-chain branches per polymer molecule were indeed found, as inferred from solution properties.     

Consequence analysis of blast wave from accidental gas explosions

Recently, consequence analyses of accidental gas explosions are often carried out to assess the risk of chemical plants, hazardous-materials sites and new energy systems. In these consequence analyses, it is indispensable to adequately predict the blast-wave (pressure-wave) intensity from gas deflagrations. Some prediction models already exist; however, most of them are based on the theory for explosives and adjusting parameters are needed for evaluating gas deflagrations. In this study, new prediction methods for gas deflagrations were developed. From theoretical analysis of blast-wave generation by a gas deflagration, an evaluation equation of the blast-wave intensity was derived. As the scale of gas deflagration becomes larger, flame front instability (especially hydrodynamic instability) would be more effective and the flame propagating velocity starts to be accelerated. Therefore, the equation was modified considering the effect of flame instability. The evaluations by this modified equation agreed well with the results of large scale experiments. By this analysis, it was found that not only total energy release but also combustion reaction rate has to be introduced into the prediction of gas deflagrations. Using this concept, a modified scale model to predict the blast-wave intensity was developed by improving the previous scale model introducing the term of combustion reaction rate as burning velocity. Furthermore, scale analysis was performed to develop the new scaling law. The universal relationship between scaled distance and overpressure has been realized by this new scaling law for gas deflagrations. In summary, these results provide new methods for accurate prediction of the blast-wave intensity from gas deflagrations.     

Polarization shift keying (POLSK) phase diversity homodyne system with multiplying detection in coherent optical communications

We propose a Polarization Shift Keying (POLSK) phase diversity homo-dyne system with multiplying detection in coherent optical communications. The proposed system uses only one of three Stokes parameters, which is the phase difference between two orthogonal polarizations. Although such systems using only one Stokes parameter are very sensitive to polarization fluctuation, the proposed system becomes insensitive to the linear polarization fluctuation by using the multiplying detection with a combination of in-phase and quadrature optical signal components on two orthogonal polarizations. Furthermore, insensitivity to phase noise and offset frequency and attractiveness due to homodyne type in high-speed transmissions are maintained. The most attractive feature of the proposed system is that neither a polarization controller nor electronic feedback loop for matching the state of polarization (SOP) between transmitted and local oscillator (LO) optical signals is needed. We theoretically analyze the receiver sensitivity and the power penalties of the proposed system for the cases of the elliptical SOP of received optical signals and the imbalance optical 90° hybrid.     

Chiral separation by electrokinetic capillary chromatography using newly synthesized linear polymers containing L-amino acid moieties.

Chiral linear polymers were prepared by the thermal polymerization of N-acryloyl-L-valine and N-acryloyl-L-alanine derivatives using 3-mercaptopropionic acid (3-MPA) as a radical transfer agent. C-Terminal groups of the derivatives were methyl and tert-butyl esters later removed, and N-methylamide moieties. The N'-methylamide derivative of N-acryloyl-L-valine was copolymerized with methyl ester at a molar mixing ratio of 1:1. The ester groups were removed to provide anionic linear polymers terminated with carboxylic acid of the amino acid residue. The polymers are thus shown to function as pesudostationary phases that separate enantiomeric solutes in electrokinetic capillary chromatography (EKC). Racemic 3,5-dinitrobenzoylamino isopropyl esters were separated with the polymer derived from N-acryloyl-L-valine esters and with the copolymer from N-acryloyl-L-valine methyl ester and N-acryloyl-L-valine N'-methylamide at pH 7.0. These separations could not be observed at pH 9.0 in migrating solutions containing anionic linear polymers. This pH dependence can be discussed from the standpoint of the microscopic hydrophobicity of the polymers, as assessed from the fluorescence of pyrene adsorbed onto the polymers in water.     

Remark on a toroidal detector of a gravitational wave

The object of this paper is to review the detector of a gravitational wave that was proposed by Braginsky and Mensky (1971). The derivation of the sensitivity is based on the same assumption as they proposed. It is concluded that the phase difference is linear in time and that the sensitivity of this detector is different from the result claimed by Braginsky and Mensky. The foundation to obtain the phase difference, i.e., the sensitivity, in this paper is not the frequency as they used but rather the movement of the wave front in the detector.     

Effects of a static electric field upon dielectric properties of poly(vinylidene fluoride) and poly(vinyl fluoride)

Dielectric measurements on poly(vinylidene fluoride) at higher temperatures result in anomalously large values of ε′ and ε″ at lower frequencies. When a static field is applied, a drastic decrease of ε′ and ε″ occurs. The effects of a static field can be summarized as follows: (1) the field effect upon ε′and ε″ is more significant at lower frequencies; (2) with increasing field strength, the rate of decrease of ε′and ε″ with time becomes greater and the ultimate values are smaller; (3) when the field is removed, ε′and ε″ recover but the ultimate recovery is incomplete; (4) the field effect depends strongly on temperature. Such behavior seems to be attributable to the displacement of ionic impurities and to their electrolysis. These results provided a method to remove the contribution of ionic impurities to ε′and ε″ and to measure the relaxation process due only to dipoles of a polymer. The application of this method revealed the dielectric high temperature absorption which had been masked by the ionic conduction in poly(vinyl fluoride).