Synthesis of spherical and hemispherical sugar‐containing poly(ornithine) dendrimers

A novel sugar‐containing poly(ornithine) dendrimer is synthesized for possible antigen delivery and related applications. The dendrimer contains an ornithine dendron as interior scaffolding and oligosaccharides on the periphery, which provide an attachment site for a peptide antigen. Maltose or lactose is bound to both hemispherical and spherical poly(ornithine) dendrimer generation 3 (G3) by reductive amination between its reducing end and the peripheral amino group of the dendrimer using a borane‐pyridine complex in a buffer solution at 50 °C. The degree of substitution of sugar is changed by varying the molar ratio of sugar to dendrimer. When the surface of spherical poly(ornithine) dendrimer G3 is modified by binding β‐alanine to the 16 amino groups, highly substituted maltose‐ or lactose‐β‐alanine‐poly(ornithine) dendrimer G3 is obtained in high yield after 7 days of reaction. The structures of these sugar‐containing dendrimers are characterized by NMR and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry analyses. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1400–1414, 2004     

Synthesis and properties of novel 1,1‐difluoropropoxy‐linked liquid crystalline compounds of negative dielectric anisotropy

A series of liquid crystalline compounds having the difluoropropyleneoxy moiety (–OCF₂C₂H₄–) as a linking group has been synthesized. The physical properties, i.e. dielectric anisotropy, birefringence, viscosity and phase transition temperatures, have been measured. This novel class of compounds shows a larger negative dielectric anisotropy than the corresponding compounds having a propyleneoxy (–OC₃H₆–) linking group. Their dielectric properties may be explained by the combined effect of fluorine atoms with large electron negativities and the electron donating feature of an oxygen atom substituted on the same carbon atom. The semi‐empirical quantum calculation method (AM1) also confirmed this dielectric behaviour of the difluoropropyleneoxy linkage group.     

Scanning tunneling microscope light emission spectra of polycrystalline Ge2Sb2Te5 and Sb2Te3

We have observed scanning tunneling microscope light emission (STM-LE) spectra of Ge₂Sb₂Te₅ and Sb₂Te₃. Although these chalcogenide alloys exhibit band gaps less than 0.5 eV, the STM-LE was observed with a narrow spectral width at a photon energy of 1.5 eV for both materials. By analyzing its bias voltage, polarity, and temperature dependencies combined with recently reported theoretical electronic structures, we concluded that the STM-LE is excited by electronic transitions taking place in the local electronic structure having a direct gap-like shape with a band gap of 1.5 eV, commonly found in the electronic structures of both materials.     

Diffusion process of electrons injected from STM tip into AlGaAs/GaAs quantum wells

We have investigated the electron diffusion process in Al_0.3Ga_0.7As/GaAs quantum well (QW) structures by means of scanning tunneling microscope light emission (STM-LE) spectroscopy. The optical measurements were performed on a cleaved (1 1 0) surface at room temperature. The STM-LE spectra were measured by injecting hot electrons from the tip positioned at different distances from the QWs. The emission intensity from individual wells as a function of the tip-well distance was found to decay with two distinct decay constants. From comparison with Monte Carlo simulations for hot electron relaxation, we found that the intervalley scattering from the Γ valley to the L and X valleys has the most significant effect on the diffusion process of the injected electrons.     

Chemo-enzymatic production of fuel ethanol from cellulosic materials utilizing yeast expressing β-glucosidases

Ethanol was produced in a considerably high yield by fermenting hydrolyzates from cellulosic materials by means of a recombinant laboratory yeast expressing β-glucosidases. Tissue paper, cotton, and sawdust were hydrolyzed by two-step sulfuric acid hydrolysis to give mixtures containing glucose, cellobiose, and higher cello-oligosacc arides. After the cellulosic material was partially hydrolyzed with 80% sulfuric acid, the hydrolysis was continued with 5% sulfuric acid. Except for non-carbohydrate components, all constitutents in the hydrolyzates were fermented by the yeast that was preincubated in the medium that the plasmid encoded by the β-glucosidases gene was kept in the muliplicated yeast. A solution containing 4% hydrolyzates from paper was fermented to give as high as 1.9% maximum ethanol concentration and 70% ethanol conversion. Cotton also gave a similar result. Sawdust was converted into ethanol in approx 22% conversion. Accordingly, it was revealed that the β-glucosidases-expressing yeast can ferment the cello-oligosaccharides obtained by hydrolysis of cellulosic materials into ethanol. In addition, a hydrolyzate containing a high glucose proportion gave a high ethanol concentration in a short time.     

Chemically stabilized phenylboranylidene groups having a dimethoxytrityl group as a colorimetrically detectable protecting group designed for cis-1,2-diol functions of ribonucleosides in the solid-phase synthesis of m2(2,2)G5'ppT

To not only improve the inherently poor stability of the phenylboranylidene group as a protecting group of the 2',3'-cis-diol function of ribonucleosides but also introduce a colorimetrically detectable function into its mother structure, various 2-[(dialkylamino)methyl]phenylboronic acid derivatives having a [(4,4'-dimethoxytrityl)oxy]methyl group were synthesized. The reaction of uridine with these substituted phenylboronic acid derivatives gave the corresponding 2',3'-O-phenylboranylideneuridine derivatives. The stability of these phenylboranylidene groups was examined. As a result, it was shown that the steric hindrance around the amino group greatly influenced the stability of the 2-substituted phenylboranylidene groups. The 2-aminomethyl-5-[[(4,4'-dimethoxytrityl)oxy]methyl]phenylboranylidene group was the most stable. Its 2-dimethylamino counterpart, the 2-[(dimethylamino)methyl]-5-[[(4,4'-dimethoxytrityl)oxy]methyl]phenylboranylidene group, was the second most stable. When the most and second stable protecting groups were applied to the synthesis of m(2)(2,2)G(5)(')ppT on controlled pore glass, the second stable protecting group showed the best result. The use of this DMTr-containing protecting group enabled us to estimate colorimetrically the amount of the m(2)(2,2)G residue that was incorporated into the reactive site of the pT-loaded CPG resin.     

Detection of the frustrated rotation mode of CO on Cu(0 0 1) by very low energy photoelectron spectroscopy

We have measured the very low energy photoelectron spectra of the clean and CO covered Cu(0 0 1) surfaces at low temperature (15 K). A step at 34.5 meV below the Fermi level appeared in the CO/Cu(0 0 1) spectra, while no structure was found at the same position in the clean Cu(0 0 1) spectrum. Furthermore, we have succeeded in measuring the spectral shift of the step to 33.2 meV below the Fermi level by isotopic substitution of the CO molecule. We have concluded that this step originates from the inelastic scattering of photoelectrons through excitation of the frustrated rotation mode of the CO molecule.     

Liquid-like Raman scattering by superionic materials

The Raman spectrum of a superionic conductor, α-AgI, is compared with the spectra of the melt of AgC$\text{l}$ and AgBr, in order to determine the responsible Raman processes. We conclude that because of the strong anharmonicity and high translational disorder in superionic conductors, spectra analyses based on the concept of harmonic lattice are unsuitable. A dynamical picture of ions similar to that of liquids appears to be more useful than the phonon concepts.