ACTA POL YMERICA SINICA

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1 ACTA POL YMERICA SINICA No. 1 Feb., ( ) ( ) (CS1 CS2). GPC gπmol. 622 ( ), % 36 %( WΠW %),. KS, KS.,,.,,, ( ) [1 ].. 20,.,.,. 6,,, [2 ] ;, [3 ] ;,, ; [4 ] ;, [5 ] Ogura [6 ] Π10 % 40 %,, [7 16 ]., [17 19 ], 20 ( 3220 gπmol),,.,, , ( ). CS1 CS2, 83 % 88 %( ). Olympus BH2 ; 2 Esquire 3000 Plus ; ATAGO 1T ; Varian UNITY 500 Hz ; Agilent 1100 ; ( GPC), Ultra hydrogel TM 250, 30, 012 molπl HAc2011 molπl NaAc, 018 mlπmin. D2 ( M = 179) ( M = 501) ( M = 5900,11800,22800) ml 1 % Π,, 1.,, , ; ( ), ( E ) ( 2004I006) ; 33,E2mail xmu. edu. cn 16

2 1 : 17 c [20 ],,,., [ 21 ] 4,,, ,, GPC 6000,. GPC : , 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 ( min, 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.

3 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 CS CS , , 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 (LΠ2 q) ( LΠ2 q) 2 ( LΠ2 q) [ (LΠ2 q) ] (1) L = L 0 MΠM 0, d,l ( ), q ( q = 22 nm [17 ] ). d : d = M 0 N A L (2)

4 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 = 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) (CS2) CS1 CS2 2, 622, 100 %,., KS.,,. 2, 700 KS 100 %, KS.. KS Kratky2Porod,,.,,. T N2I,, [25,26 ],,. Onsager Flory KS,,. [27 ], wt % 32 wt %, KS 3211 % , KS KS. 14 ( 2311) KS, 4 ( 622) KS. KS, ( 4000),.,,,.

5 REFERENCES 1 Jiang Tingda ( ). Chitin( ). Beijing( ) :Chinese Chemistry Industry Press( ), Kjell M V,Marit W A,Hans G. Carbohydr Res,1991,211 : 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) : Yan Qin( ),Shen Yuexin( ),Wang Zao ( ). Food Research and Development ( ),2003,24 (2) : 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, Rout D K,Pulapura S K,Gross R A. Macromolecules,1993,26 : Dong Yanming( ),Li Zhiqiang( ),Guo Rong( ). Chem J Chin Univ( ),1998,19 (1) : Dong Yanming( ),Li Zhiqiang( ). Chemistry( ),1998, (6) : Dong Yanming( ),Li Zhiqiang( ). Chem J Chin Univ ( ),1998,19 (8) : Dong Y M,Yuan Q,Wu Y S,Wang M.J Appl Polym Sci,2000,76 : Dong Y M,Wu Y S,Wang J W,Wang M. Euro Polym J,2001,37 : Wu Y S,Dong Y M,Chen L,Huang J Y. Macromol Biosci,2002,2 : Wu Y S,Dong Y M,Zhou H,Ruan Y H,Wang H W,Zhao Y Q.J Appl Polym Sci,2003,90 : Dong Yanming( ),Wu Yusong( ),Ruan Yonghong( ),Wang Huiwu( ),Zhao Yaqing( ). Acta polymerica Sinica ( ),2003, (4) : Dong Yanming( ),Wu Yusong( ),Ruan Yonghong( ),Zhao Yaqing( ),Wang Huiwu( ),Zhou Hua ( ). Acta Polymerica Sinica ( ),2003, (5) : Terbojevich M,Cosani A,Conio G,Marsano E,Bianchi E. Carbohydr Res,1991,209 : Hu Zhongming( ),Li Ruixia ( ),Wu Dacheng( ),Liu Hongbin ( ),Sun Yushan ( ),Wu Liheng( ). Acta polymerica Sinica ( ),2000, (1) : Dong Y M,Qiu W B,Ruan Y H,Wu Y S,Wang M,Xu C Y. Polym J,2001,33 : Tseng S L,Valente A. Gray D G. Macromolecules,1981,14 : Huang Yong( ),Chen Mingcai ( ),Li Lisheng( ). Chemistry Communication( ),1986, (4) : Khokhlov A R,Semonov A N. Physica,1981,108A(2Π3) : Khokhlov A R,Semonov A N. Physica,1982,112A(3) : Sakurai K,Takahashi T,Kimura K,Takahashi T. Sen2I Gakkashi,1982,41 (9) :T2361 T Wang Liangyu( ),Liao Songsheng( ).Liquid Crystalline Chemistry ( ). Beijing ( ) : Chinese Science Press ( ), Xie Yuzhang( ).Liquid Crystalline Physics ( ). Beijing( ) :Chinese Science Press( ), Dong Y M,Wang H W,Zheng W Y,Zhao Y Q,Bi D X. Cabohydrate Polymers,2004,57 : 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 ) ( 2 Haidebei Marine Biological Product Co. Ltd., Jinan ) 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