1 2006 2 ACTA POL YMERICA SINICA No. 1 Feb., 2006 3 1 33 1 1 1 1 1 2 ( 1 361005) ( 2 250022) (CS1 CS2). GPC 622 2311 gπmol. 622 ( ), 622 2311 73 % 36 %( WΠW %),. KS, KS.,,.,,, ( ) [1 ].. 20,.,.,. 6,,, [2 ] ;, [3 ] ;,, ; [4 ] ;, [5 ]. 1982 Ogura [6 ] Π10 % 40 %,, [7 16 ]., [17 19 ], 20 ( 3220 gπmol),,.,,.. 1 111, ( ). CS1 CS2, 83 % 88 %( ). Olympus BH2 ; 2 Esquire 3000 Plus ; ATAGO 1T ; Varian UNITY 500 Hz ; Agilent 1100 ; 112 11211 ( GPC), Ultra hydrogel TM 250, 30, 012 molπl HAc2011 molπl NaAc, 018 mlπmin. D2 ( M = 179) ( M = 501) ( M = 5900,11800,22800). 11212 1 ml 1 % Π,, 1.,, 20 3 2004207227,2004212227 ; ( 20374041), ( E0310002) ( 2004I006) ; 33,E2mail :ymdong @jingxian. xmu. edu. cn 16
1 : 17 c 3. 11213 [20 ],,,., [ 21 ] 4,,,. 2 211,, GPC 6000,. GPC : 501. 1., 50211, 50211, [M + H] +,,.,,. CS1 GPC 2 ;CS2 GPC 3. Fig. 1 Mass spectra of trisaccharides Fig. 2 GPC trace (a) and mass spectra (b) of CS1 CS1 GPC ( 101751 min, 111940 min ) M n = 622 gπmol, M w = 946 gπmol.,, [M + H] + = 663, 662 gπmol, GPC, GPC ( :, M n ). M n M w,., CS2 GPC M n = 2311 gπmol, M w = 6570 gπmol, CS2 GPC CS1 GPC.
18 2006 Fig. 3 GPC trace (a) and mass spectra (b) of CS2, 970, 3270, GPC M n.,, CS1 CS2 GPC M n ( 1). Sample Table 1 The molecular masses of CS1 and CS2 GPC M n (gπmol) M w (gπmol) d MS (gπmol) Values Degree of adaptedpolymerization CS1 622 946 1152 662 622 4 CS2 2311 6570 2184 971,3274 2311 14 212, 622 ( )., 90 %. 4 CS1 90 %.,, 5 CS2 60 %.. Fig. 4 Photomicrograph of the planar texture observed in the 90 wt % CS1 aqueous solution Fig. 5 Photomicrograph of the planar texture observed in the 60 wt % CS2 aqueous solution, CS1 = 73 wt %,CS2 = 36 wt %., 6.,,, CS1 = 72 % ;CS2 = 36 %.. 213, Khokhlov Semenov KS [22,23 ]. KS, : V 2 = d 2 q 3134 + 11194 (LΠ2 q) + 6134 ( LΠ2 q) 2 ( LΠ2 q) [1 + 01586 (LΠ2 q) ] (1) L = L 0 MΠM 0, d,l ( ), q ( q = 22 nm [17 ] ). d : d = M 0 N A L 0 1 2 (2)
1 : 19 Fig. 6 Measurements of c 3 by refractometry for a CS1Π water solution (a) and a CS2Πwater solution (b) M 0 ( 161), ( 115 gπcm 3 ), N A Avogadro, L 0 ( b = 11030 nm [24 ] ). KS 2. Table 2 The calculated data for critical concentration of chitosan and chitosan2oligosaccharides in water according to KS theory M L (nm) LΠ2 q V 2 ( %) c 3 ( %) 622 (CS1) 119896 010452 11212-708 212647 010515 10010 10010 1000 31199 010727 7418 8117 2000 61398 011454 4412 5413 2311(CS2) 713923 011680 40100 5010 2500 71997 011817 3810 4719 3000 91596 012181 3410 4316 4000 121795 012908 28188 3719 5000 151994 013635 2518 3413 8000 25159 015816 2113 2819 1 10 4 311988 01727 1918 2710 5 10 4 1591938 31635 1513 2113 10 10 4 3191876 7127 1419 2018 20 10 4 6391752 14154 1417 2015 CS1 CS2 2, 622, 100 %,., KS.,,. 2, 700 KS 100 %, KS.. KS Kratky2Porod,,.,,. T N2I,, [25,26 ],,. Onsager Flory KS,,. [27 ], 4304 31 wt % 32 wt %, KS 3211 %. 1 10 4, KS 4300. KS. 14 ( 2311) KS, 4 ( 622) KS. KS, ( 4000),.,,,.
20 2006 REFERENCES 1 Jiang Tingda ( ). Chitin( ). Beijing( ) :Chinese Chemistry Industry Press( ),2003. 1 21 2 Kjell M V,Marit W A,Hans G. Carbohydr Res,1991,211 :17 23 3 Du Yuguang( ),Zhang Mingjun( ),Zhang Hu( ). Chinese Journal of microbioelogy( ),2001,13 (1) :5 7 4 Xia Wenshui ( ),Wu Yannan( ).Journal of Wuxi Light Industry University( ),1996,15 (4) :297 302 5 Yan Qin( ),Shen Yuexin( ),Wang Zao ( ). Food Research and Development ( ),2003,24 (2) :26 29 6 Ogura K,Kanamoto T,Sannan T,Tanaka K,Iwakura Y. In : Hirano S,Tokura S,eds. Chitin Chitosan Proceeding International Conference 2nd. Tottori : Jpn Soc Chitin Chitosan,1982. 39 44 7 Rout D K,Pulapura S K,Gross R A. Macromolecules,1993,26 :5999 6006 8 Dong Yanming( ),Li Zhiqiang( ),Guo Rong( ). Chem J Chin Univ( ),1998,19 (1) :161 163 9 Dong Yanming( ),Li Zhiqiang( ). Chemistry( ),1998, (6) :39 42 10 Dong Yanming( ),Li Zhiqiang( ). Chem J Chin Univ ( ),1998,19 (8) :1343 1345 11 Dong Y M,Yuan Q,Wu Y S,Wang M.J Appl Polym Sci,2000,76 :2057 2061 12 Dong Y M,Wu Y S,Wang J W,Wang M. Euro Polym J,2001,37 :1713 1720 13 Wu Y S,Dong Y M,Chen L,Huang J Y. Macromol Biosci,2002,2 :131 134 14 Wu Y S,Dong Y M,Zhou H,Ruan Y H,Wang H W,Zhao Y Q.J Appl Polym Sci,2003,90 :583 586 15 Dong Yanming( ),Wu Yusong( ),Ruan Yonghong( ),Wang Huiwu( ),Zhao Yaqing( ). Acta polymerica Sinica ( ),2003, (4) :509 512 16 Dong Yanming( ),Wu Yusong( ),Ruan Yonghong( ),Zhao Yaqing( ),Wang Huiwu( ),Zhou Hua ( ). Acta Polymerica Sinica ( ),2003, (5) :685 687 17 Terbojevich M,Cosani A,Conio G,Marsano E,Bianchi E. Carbohydr Res,1991,209 :251 260 18 Hu Zhongming( ),Li Ruixia ( ),Wu Dacheng( ),Liu Hongbin ( ),Sun Yushan ( ),Wu Liheng( ). Acta polymerica Sinica ( ),2000, (1) :46 49 19 Dong Y M,Qiu W B,Ruan Y H,Wu Y S,Wang M,Xu C Y. Polym J,2001,33 :387 389 20 Tseng S L,Valente A. Gray D G. Macromolecules,1981,14 :715 719 21 Huang Yong( ),Chen Mingcai ( ),Li Lisheng( ). Chemistry Communication( ),1986, (4) :1 5 22 Khokhlov A R,Semonov A N. Physica,1981,108A(2Π3) :546 556 23 Khokhlov A R,Semonov A N. Physica,1982,112A(3) :605 614 24 Sakurai K,Takahashi T,Kimura K,Takahashi T. Sen2I Gakkashi,1982,41 (9) :T2361 T2368 25 Wang Liangyu( ),Liao Songsheng( ).Liquid Crystalline Chemistry ( ). Beijing ( ) : Chinese Science Press ( ),1988. 132 178 26 Xie Yuzhang( ).Liquid Crystalline Physics ( ). Beijing( ) :Chinese Science Press( ),1988. 9 14 27 Dong Y M,Wang H W,Zheng W Y,Zhao Y Q,Bi D X. Cabohydrate Polymers,2004,57 :235 240 STUDIES ON CHITIN2BASED L IQUID CRYSTALL INE POLYMERS THE LYOTROPIC LIQUID CRYSTALLINITY OF LOW MOLECULAR WEIGHT CHITOSAN AND THE INFL UENCE OF MOLECULAR MASS ON CRITICAL CONCENTRATION DONG Yanming 1, HUANG Xunting 1, ZHAO Yaqing 1, YANGLiulin 1, MAO Wei 1, BI Danxia 1, ZHAO Lianjun 2 ( 1 Department of Materials Science and Engineering, Xiamen University, Xiamen 361005) ( 2 Haidebei Marine Biological Product Co. Ltd., Jinan 250022) Abstract The lyotropic liquid crystallinity of two low molecular weight chitosan samples prepared by enzymic decomposition was investigated. The number averge molecular masses of those two samples CS1 and CS2 were 622 and 2311 gπmol,measured by means of GPC and MS. The lyotropic liquid crystalline behavior was found for these samples even when the molecular mass was as low as 622 gπmol ( tetramer). The critical concentration of CS1 and CS2 to form liquid crystalline phase was determined to be 73 wt % and 36 wt % respectively. The results agree with the principle rule deduced from chitosans with high and medium molecular mass,which states that the critical concentration increases with the decrease of molecular mass. However the results were not accordant with those predictd by the traditional Khokhlov2Semenov( KS) theory,because the molecular mass of the samples is out of the region in which KS theory can be used. Key words Low molecular weight chitosan, Lyotropic liquid crystals, Critical concentration