• Journal of the Korean Chemical Society
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• v.46 no.5
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• pp.479-485
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• 2002

• Polymer(Korea)
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• v.28 no.1
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• pp.92-102
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• 2004

(6-Cholesteryloxycarbonylpentoxypropyl)celluloses (CHPCs) with degree of esterification (DE) ranging from 2.25 to 2.91 were synthesized by reacting hydroxypropyl cellulose with 6-cholesteryloxycarbonylpentanoyl chloride. The acrylic esters of CHPCs (CHPCEs) and their photocrosslinked films with liquidcrystalline order were also synthesized. The thermotropic properties of mesophase for both uncrosslinked and crosslinked samples and the swelling behavior of the crosslinked samples in acetone were investigated. The hydroxypropyl cellulose exhibited an enantiotropic cholesteric phas, while all the uncrosslinked cholesterylbearing samples exhibited a monotropic cholesteric phases; the 6-cholesteryloxycarbonylpentanoyl chloride also showed a monotropic smectic phase. The hydroxypropyl cellulose formed a right-handed helix whose optical pitch (λ$\sub$m/) increases with temperature, whereas all the uncrosslinked derivatives farmed left-handed helices whose λ$\sub$m/'s decreased with temperature. The thermal stability of the mesophase and the magnitude of λ$\sub$m/ at the same temperature for both CHPCs and CHPCEs decreased with increasing DE. All the crosslinked samples, in constrast with CHPCEs, did not display reflection colors but exhibited an anisotropic swelling characteristic of crosslinked gel retaining liquid-crystalline order.

• Polymer(Korea)
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• v.28 no.1
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• pp.41-50
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• 2004

A new hydroxypropyl chitosan capable of forming a thermotropic liquid crystalline phase and two kinds of derivatives based on the hydroxypropyl chitosan (6-cholesteryloxycarbonylpentoxypropyl) chitosans (CHPCTs) and acrylic acid esters of CHPCT (CHPCTEs) were synthesized. The crosslinked films with liquid crystalline order were also prepared by photocrosslinking CHPCTE in mesophase. The liquid crystalline properties for all the samples and the swelling behavior of the crosslinked samples in acetone were investigated. In contrast with the hydroxypropyl chitosan, all the uncrosslinked cholesteryl-bearing samples farmed monotropic cholesteric phases with left-handed helicoidal structures and exhibited reflection colors over the full cholesteric range. This is the first report of a thermotropic cholesteric liquid crystalline chitosan derivative with reflection bands in the visible region. Both the optical pitches (λ$\_$m/'S) of CHPCT and CHPCTE decrease with temperature or with cholesteryl content at a given temperature. However, the λ$\_$m/ of CHPCT was larger than that of CHPCTE at the same temperature and at the same cholesteryl content. All the crosslinked samples did not display reflection colors, indicating that the cholesteric structure of CHPCTE significantly changes upon crosslinking. The two-dimentional anisotropic swelling characteristic of liquid crystalline networks was observed for all the crosslinked samples.

• Polymer(Korea)
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• v.28 no.6
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• pp.531-537
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• 2004

Various half-ester acrylates were prepared from anhydrides and 2-hydroxyethyl acrylate. Photocurable epoxy modified acrylates were prepared from synthesized half-ester acrylate and neopentylglycol diglycidylether. Physical properties such as hardness, yellowing, tensile strength and elongation were tested and compared as the structure of oligomer in cured-film differs. It was found that viscosity of neopentylglycol diglycidylether-hexahydrophthalic anhydride (NP-HA) was highest. Hardness and tensile strength of photocrosslinked neopentylglycol diglycidylether-hexahydrophthalic anhydride were better than those of other photocrosslinted epoxy acrylates. And 5% weight loss temperature of photocrosslinked neopentylglycol diglycidylether-hexahydrophthalic anhydride was higher than those of other photocrosslinked epoxy acrylates. Value of yellow index of photocrosslinked neopentylglycol diglycidyl ether-succinic anhydride (NP-SA) was lower than the other products.

• Applied Chemistry for Engineering
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• v.25 no.4
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• pp.392-395
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• 2014

(2S,3S,4S)-3,4-Dihydroxyglutamic acid (DHGA), a biologically active ${\alpha},{\beta}$-dihydroxy-${\gamma}$-amino acid, was efficiently synthesized from a readily available D-serine derivative in 30% overall yield over 11 steps. The key stereoselective $OsO_4$-catalyzed dihydroxylation reaction controlled by an N-diphenylmethylene group on the amino group of ${\gamma}$-amino-${\alpha},{\beta}$-unsaturated (Z)-ester successfully introduced the diol moiety of the intermediate 5a in 86% with more than 10 : 1 diastereomeric ration. Then it was in turn successfully converted to the desired target compound, (2S,3S,4S)-3,4-DHGA, via simple oxidation and hydrolysis in a highly stereoselective manner and a higher yield than the previous syntheses. This result strongly supports that our synthetic methodology of stereoselective $OsO_4$-catalyzed dihydroxylation should be useful in stereoselctive synthesis of various bioactive compounds with an amino diol moiety.

• Applied Chemistry for Engineering
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• v.27 no.5
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• pp.490-494
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• 2016

This paper describes the very efficient and highly enantioselective ring opening of terminal epoxides with alkyl and arene sulfonic acid. The dinuclear chiral (salen) Co complexes bearing Lewis acids of Al, Ga and In catalyze the reaction enantioselectively in the presence of tetrabutylammonium chloride using tert-butyl methyl ether as a solvent. The variation of the anion of the tetra butyl ammonium salt has significant impact on the reactivity and selectivity of the asymmetric ring opening of phenyl glycidyl ether with p-toluenesulfonic acid. The order of reactivity and selectivity was found to be $Cl^-$ > $l^-$ > $Br^-$ > $OH^-$. Strong synergistic effects of the different Lewis acid centers of Co-Al, Co-Ga and Co-In complexes were observed in the catalytic process. The dinuclear chiral salen catalyst containing $AlCl_3$ was found to be most active and highly enantioselective (91% ee).