Synthesis of a Sialic Acid Containing Complex‐Type N‐Glycan on a Solid Support

On solid ground : A new solid‐phase synthesis of N‐linked glycans featuring 1) highly stereoselective β‐mannosylation and microfluidic α‐sialylation and 2) efficient glycosylation of the N‐phenyltrifluoroacetimidate units on JandaJel resin is reported. Reagent concentration effects by a fluorous solvent are effectively applied, and the use of these methods results in the first synthesis of a sialic acid containing complex‐type N‐glycan on a solid support.

     

Structural scaffold of 18-crown-6 tetracarboxylic Acid for optical resolution of chiral amino acid: x-ray crystal analyses of complexes of D- and L-isomers of serine and glutamic acid

(+)-18-crown-6 tetracarboxylic acid (18C6H4) has been used as a chiral selector for D/L-amino acids in HPLC, where L-isomer is usually eluted prior to D-isomer, except for the case of serine. To clarify why serine exhibits the reverse order for the elusion, the chiral interactions of D- and L-serines with (+)-18C6H4 were investigated by the X-ray single crystal analyses, together with the case of D- and L-glutamic acids, which exhibit the usual elution order in HPLC. The backbone structures (amino, Calpha-H and carboxyl groups) of these four amino acids showed the nearly same interaction with (+)-18C6H4 despite their different chirality. In contrast, the hydroxyl group of L-serine side chain formed a hydrogen bond with the carboxyl group of (+)-18C6H4, whereas such a interaction was not formed for the side chain of D-serine and D- and L-glutamic acids. Thus, it was shown that the exception of D/L-serine from the first elution rule of L-isomer in HPLC is due to the presence and absence of a hydrogen bond formation of its side chain OH group.     

Structural scaffold of 18-crown-6 tetracarboxylic acid for optical resolution of chiral amino acid: X-ray crystal analyses and energy calculations of complexes of D- and L-isomers of tyrosine, isoleucine, methionine and phenylglycine

To clarify the structural scaffold of (+)-18-crown-6 tetracarboxylic acid ((+)-18C6H4) for the optical resolution of a chiral amino acid, the crystal structures of its equimolar complexes with L- and D-isomers of tyrosine (Tyr), isoleucine (Ile), methionine (Met) and phenylglycine (PheG) were analysed by X-ray diffraction methods. (+)-18C6H4 took very similar conformations for all complexes. Although the chemical structure of (+)-18C6H4 is C2-symmetric, it took a similar asymmetric ring conformation of radius ca. 6.0 A. In all complexes, the amino group of chiral amino acids was located near the center of the ring and formed three hydrogen bonds and five electrostatic interactions with eight oxygen atoms of the ether ring and carboxyl groups. Also, the Calpha atom of chiral amino acids participated in Calpha-H...O interaction with the oxygen atom of (+)-18C6H4. In contrast, the carboxyl group of chiral amino acids did not directly interact with (+)-18C6H4. These results indicate that the structural scaffold of (+)-18C6H4 for the optical resolution of chiral amino acids is mainly based on the mode of interaction of (+)-18C6H4 with the amino and Calpha-H groups of chiral amino acids. The differences in interaction pattern and binding energy between the L- and D-isomers of each amino acid are discussed in relation to the chiral recognition of (+)-18C6H4.     

Numerical analysis of fatigue striations

A computational model was developed to numerically analyse fatigue striations. The inclined strip yield model with continuous distributions of infinitesimal dislocations was utilized to express the crack tip plasticity in this model. The fatigue crack tip blunting process was approximated by sequential activation of two slip lines under loading, and crack closure during unloading was taken into account. The plastic zone at a growing fatigue crack tip at the maximum load was independent of the crack growth up to ten cycles while the reversed plastic zone decreased in a size to one twentieth of that at the maximum load as the crack grew. The ratio of these plastic zone sizes and also the crack tip opening displacement were quite different from the simple prediction by J.R. Rice for a stationary crack. The computed striation spacings were compared with the observed ones and moderate agreement between them obtained.     

Stabilized generation of wavelength conversion by using high-accurate self-phase modulation based all-optical limiter

We demonstrate stable wavelength conversion by using our proposed high-accurate all-optical limiter based on self-phase modulation (SPM) with preventing serious influences of input intensity fluctuation. Wavelength conversion is one of the typical non-linear optical signal processing for the next generation of photonic networks. And it is very sensitive to input intensity fluctuation. To prevent serious influences of intensity fluctuation, it is necessary for intensity fluctuation compensation technique with high-accurate limiting function. To pursue high-accurate limiting function, we have proposed a new approach: applying pre-chirping pulses before inputting to the SPM fiber. By using our proposed limiter, the stabilization of the wavelength conversion is significantly improved, and we confirm that our proposed limiter is very effective for the stabilization of subsequent wavelength conversion processing.     

Efficiency improvement of optical pattern recognition in ultra-fast all-optical intensity equalizer

To cope with a larger intensity fluctuation of optical signals in optical communication networks, we have proposed and demonstrated an ultra-fast all-optical intensity equalizer based on an optical pattern recognition technique. To achieve higher transfer efficiency for this equalizer, we designed and fabricated a highly-efficient optical amplitude-phase filter using a diffractive optical element for optical pattern recognition. The fabricated amplitude-phase filter provides a diffraction efficiency of 85%, and the all-optical intensity equalizer is demonstrated to have higher transfer efficiency, when this filter is used.     

Thermophysical and heat transfer properties of phase change material candidate for waste heat transportation system

A waste heat transportation system––trans-heat (TH) system––is quite attractive that uses the latent heat of a phase change material (PCM). The purpose of this paper is to study the thermophysical properties of various sugars and sodium acetate trihydrate (SAT) as PCMs for a practical TH system and the heat transfer property between PCM selected and heat transfer oil, by using differential scanning calorimetry (DSC), thermogravimetry-differential thermal analysis (TG-DTA) and a heat storage tube. As a result, erythritol, with a large latent heat of 344 kJ/kg at melting point of 117°C, high decomposition point of 160°C and excellent chemical stability under repeated phase change cycles was found to be the best PCM among them for the practical TH system. In the heat release experiments between liquid erythritol and flowing cold oil, we observed foaming phenomena of encapsulated oil, in which oil droplet was coated by solidification of PCM.     

Application of photopolymer to core‐hair type microgels with various hair length

The new microgels, called “core‐hair” type microgels, were synthesized. They have a hair moiety consisting of the oxyhexano‐1,7‐diyl (? O? (CH₂)₅? C(O)? ) group as a spacer and the acryloyl group for polymerization. The hair length depends on the number of spacer units, and affects the viscosity and the thixotropy index of the microgel. These core‐hair microgels show the pseudo‐plastic flow of a non‐Newtonian fluid with moderate to high dispersibility in water or alcoholic solvents. Due ­to their viscosities and dispersibilities, these core‐hair microgels are useful for photopolymer, e.g. for screen printing. Therefore, these microgels were actually applied to screen printing and confirmed pattern forming on a screen printing plate through water development. We now discuss the relation between the viscosity, the dispersibility, the photosensitivity, and the rate of photopolymerization to the hair length of the microgel. Copyright © 2001 John Wiley & Sons, Ltd.     

New deprotection method of the 2,2,2-trichloroethoxycarbonyl (Troc) group with (Bu3Sn)2

The 2,2,2-trichloroethoxycarbonyl (Troc) group was efficiently removed in high yields with (Bu₃Sn)₂ in DMF under microwave heating. The present method was applied to deprotection of the Troc group on solid support.     

Conformational studies on peptides having chiral five-membered ring amino acid with two azido or triazole functional groups within the sequence of Aib residues

The chiral cyclic α,α-disubstituted α-amino acid, (3R,4R)-1-amino-3,4-diazido-1-cyclopentanecarboxylic acid [(R,R)-Ac₅c^dN3], was introduced into achiral α-aminoisobutyric acid (Aib) peptides. The azido groups of (R,R)-Ac₅c^dN3 in the peptides were efficiently converted into 1,2,3-triazole functional groups. FTIR, ¹H NMR, and CD spectra revealed that the dominant conformations of all peptides in solution were 3₁₀-helical structures without controlling the helical-screw sense. X-ray crystallographic analyses of peptides containing (R,R)-Ac₅c^dN3 showed that both the right-handed (P) and left-handed (M) 3₁₀-helical structures were present in the crystal state.