N,N-디아실, O-아실 키토산 올리고머의 물리화학적 특성에 관한 연구

이옥섭; 하병조; 김준오; 박성규; 이윤식

Journal of the Korean Industrial and Engineering Chemistry, Vol.8, No.3, 365-373, June, 1997

Export Citation

N,N-디아실, O-아실 키토산 올리고머의 물리화학적 특성에 관한 연구

Study of Physico-Chemical Properties of N,N-Diacyl, O-Acyl Chitosan O1igomer

이옥섭, 하병조, 김준오, 박성규, 이윤식

초록

천연 고분자인 키토산의 1차 아민기를 아질산 나트릅에 의해 oxidative-deamination 반응을 일으켜 reducing end에 알데히드기를 갖는 키토산 올리고머를 얻었으며, 이를 수소화붕소산나트륨으로 환원하여 2,5-anhydro-D-mannitol로 전환하였다. 얻어진 피토산 올리고머의 평균 중합도는 겔 투과 크로마토그래피를 통해 2정도임을 알 수 있었고, 키토산에 비해 친유성 유기 용매에 대한 높은 용해성을 나타내었다. 키토산 올리고머에 아실클로라이드를 4-디메틸아미노피리딘 촉매하에서 반응시켜 N,N-디아실, O-아실 키토산 올리고머를 합성하였다. 시차주사열량 분석을 실시한 결과 N,N-디라우로일, O-라우로일 키토산 올리고머의 경우 액정 영역을 나타내었고, 편광현미경을 통해 이를 확인할 수 있었다. X-선 회절분석 실험결과 키토산 올리고머와 달리 N,N-디라우로일, O-라우로일 키토산 올리고머는 높은 결정성 구조를 나타냄을 알 수 있었다.

Chitosan oligomer having aldehyde group at reducing end was prepared by oxidative-deamination reaction of chitosan by using sodium nitrite, and the resulting aldehyde group was redeced to 2,5-anhydro-D-mannitol group. The obtained chitosan oligomer showed an average degree of polymerization(DP) 2 by GPC analysis. It was highly soluble in lipophilic solvents. N,N-diacyl, O-acyl chitosan oligomer was obtained trom the reaction between chitosan oligomer and acyl chloride under 4-dimethoxyaminopyridine catalyst. From DSC measurement, N,N-dilauroyl, O-lauroyl chitosan oligomer showed mesophase region, which was confirmed by polarizing microscope as thermotropic liquid crystalline state. X-ray diffraction pattern revealed that N,N-dilauroyl, O-lauroyl chitosan oligomer was highly crystalline, whereas chitosan oligomer was not.

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[1] Muzzarelli RAA, "Chitin," Pergamon Press, New York (1977)

[2] Muzzarelli RAA, "Natural Chelating Polymer," Pergamon Press, New York (1973)

[3] Brine CJ, Sandford PA, Zikakis JP, "Advances in Chitin and Chitosan," Elsevier Applied Science, New York (1992)

[4] Horowitz ST, Roseman S, Blumenthal HJ, J. Am. Chem. Soc., 79, 5046 (1957)

[5] Whistler RL, Wolfrom ML, "Methods in Carbohydrate Chemistry," Vol. 1, Academic Press, New York, p. 305 (1962)

[6] Rupley JA, Biochim. Biophys. Acta, 83, 245 (1964)

[7] Nakao E, U.S. Patent, 5,312,908

[8] Allan GG, Peyron M, Carbohyd. Res., 277, 257 (1995)

[9] Allan GG, Peyron M, Carbohyd. Res., 277, 282 (1995)

[10] Sugiura M, Minoda M, Watanabe J, Miyamoto T, Polym. J., 26, 1236 (1994)

[11] Hackman RH, J. Biol. Sci., 7, 168 (1954)

[12] Perrin DD, Armmaergo WLF, "Purification of Laboratory Chemicals," 3rd Ed., Pergamon Press, Oxford (1988)

[13] Mima S, Miya M, Iwamoto R, Yoshikawa S, J. Appl. Polym. Sci., 28, 1909 (1983)

[14] Rutherford FA, Austin PR, Proc. Int. Conf. Chitin/Chitosan 1st, 182 (1978)

[15] Sannan T, Kurita K, Ogawa K, Iwakura Y, Polymer, 19, 458 (1979)

[16] Tsuji A, kinoshita T, Hoshino M, Chem. Pharm. Bull., 17, 1505 (1969)

[17] Sawicki E, Hauser HR, Stanley TW, Elbert W, Anal. Chem., 33, 93 (1961)