Synthesis of stereoregular heteropolysaccharides having amino-groups by ring-opening copolymerization of 1,6-anhydro-azido-sugar derivatives

The cationic, ring-opening copolymerization of 1,6-anhydro-2-azido-3,4-di-0-benzyl-2-deoxy-(2-ABG), -3-azido-2,4-di-0-benzyl-3-deoxy- (3-ABG), -4-azido-2,3-di-0-benzyl-4-deoxy-β-D -glucopyranose (4-ABG) with 1,6-anhydro-2,3,4-tri-0-benzyl-β-D -glucopyranose (LGTBE) was investigated with phosphorus pentafluoride as catalyst at low temperatures, giving highly stereoregular, (1→6)-α-linked copolymers with number-average molecular weights of 3.90 × 10⁴?9.27 × 10⁴. Structure and composition of the copolymers were determined by ¹H- and ¹³C-NMR spectroscopies and elemental analysis, which indicated that copolymerization occurred in a stereoregular manner to give azido groups containing (1→6)-α-linked glucopyranan derivatives. The differences in polymerizability among the three azido monomers are discussed. Regioselective reduction of three kinds of heteropolysacharide derivatives which had different quantities of azido groups at C-2, -3, or -4 position with lithium aluminum hydride and subsequent debenzylation of the copolymers with sodium in liquid ammonia produced amino-group-containing heteropolysaccharides.     

Polymerization behavior of N-(p-vinyl)phenylacrylamide

The polymerization behavior of N-(p-vinyl)phenylacrylamide, synthesized from p-aminostyrene and acryloyl chloride by means of the Schotten-Baumann reaction was studied. Due to a marked difference in electron density between the two double bonds, this monomer provided soluble polymers by both cationic and anionic polymerization procedures, the cationic and anionic polymers mainly carrying, as side chains, the acrylamide and styrene moieties, respectively. The polymerization behavior of the residual double bonds was also investigated for both polymers, leading to crosslinked, insoluble products.     

Vibrational Spectroscopy of Surface Adsorbates by Sum Frequency Generation (SFG)

The vibrational spectroscopy by way of vibrational sum-frequency generation (VSFG) has been made of formic acid adsorbed on MgO(001) surface and of n-alkyltrichlorosilanes chemisorbed on quartz plates. It was revealed that the species on the MgO surface was formate ion (HCOO⁺) with CH bonds standing vertical to the surface and that the different adsorption sites showed up on repeated cycles of adsorption-desorption processes. The results of chemisorbed films indicated that the g-t and/or g-t-g′ conformational scquences of n-alkyl chains occurred more frequently by the length of alkyl chain and that the surface hydroxyls, which are the sites of chemisorption, are ripped off by pre-exposure of substrate to oxygen plasma.     

System for coincidence measurements of the ions desorbed and projectiles scattered from noble gas solid surfaces by slow multiply charged ion impacts

We have developed a new experimental apparatus for performing coincidence measurements of the ions desorbed and projectiles scattered from the surfaces of noble gas solids by slow multiply charged ion impacts at grazing incidence angles. This simultaneously measures the desorbed ions' flight times and the scattered projectiles' charge states. We also conduct experiments on 6 keV Ar⁶⁺ impacts onto a solid Ne surface using the device.     

Cyclotron resonance in lead —I: Tipping effect of magnetic field

The cyclotron resonances in lead in field tipped geometry have been observed for large tipping angles up to 40° from the sample surfaces of the (111) and (100) planes. In addition to the resonance of the orbit ζ on a cylindrical arm of the electron Fermi surface, two new series of resonances, ζ^A and ζ^B have been found, of which the clotron masses are very close to that of ζ but which differ slightly in tipping angle dependence. The mass of ζ^A is dependent on microwave frequency, so that ζ^A is attributed to the Doppler-shifted cyclotron resonance of a non-stationary orbit near, ζ, whose location is discussed in relation to the Fermi surface model of Van Dyke. In field geometry normal to the (100) surface, two series of resonances have been observed, which are characterized as the extinction of even numbered harmonic resonances. This effect arises from the skipping orbit which has a trajectory topologically similar to a baseball seam in real space. One of these series is attributed to the orbit v around the junction of four electron arms.     

Studies on polymers containing functional groups. III. Charge-transfer interaction between quinone and aza polymers

Absorption maxima and equilibrium constants for charge-transfer complexes between quinone and aza polymers, such as poly-2-vinylpyridine, poly-4-vinylpyridine, poly-2-methyl-5-vinylpyridine, and poly-N-dimethylaminomethylacrylamide, were determined spectrophotometrically. For comparison, those for charge-transfer complexes between quinone and aza compounds, such as pyridine, methyl-substituted pyridines, quinoline, triethylamine, and dimethylaniline were also presented. It was found that the equilibrium constants for polymer complexes are always larger than those for the corresponding monomer complexes, while the time required for attaining the equilibrium was longer for polymer complexes than for monomer complexes. In the interaction between quinone and poly-N-dimethylaminomethylacrylamide, two absorption maxima which gradually shifted towards each other were observed. The same phenomenon was found in the interaction between quinone and the corresponding monomer, triethylamine.     

Mesomorphic behaviour of di[(4-substituted phenyl)esters] of aromatic dicarboxylic acids

Abstract

Some di(4-alkyloxyphenyl ester)s of aromatic dicarboxylic acids which presumably exert significant steric hindrance to molecular packing, such as di(2- and/or 3-methyl or -chloro-4-alkyloxyphenyl) 2,5-pyridinedicarboxylates, di(2- and/or 3-methyl-4-alkyloxyphenyl) 2,6-naphthalenedicarboxylates, and di(4-alkylxyphenyl) 3,5-pyrazoledicarboxylates, are shown to indicate nematic liquid-crystalline behaviour.     

Development of system and technology for m?ssbauer spectroscopic microscope

We have been developing a “M?ssbauer Spectroscopic Microscope (MSM)” which consists of a focusing lens for 14.4?keV γ-rays and a high precision X–Y stage. The measuring system both for electrons and γ-rays combined with a new M?ssbauer driver, i.e., “a moving coil actuator with a liner encoder” enables us to measure the mapping images simultaneously corresponding to different spectral components. The system has a controlling system based on a LabVIEW program and a LIST mode data acquisition system (NIKI-GLASS/A3100). To investigate a correlation between the microstructure of a sample and ⁵⁷Fe atoms, a scanning electron microscope (APCO/Mini-EOC) is also installed to this system.