O,O-双十二酰化壳寡糖的溶解性能及固态结构_李凤红.pdf 4页VIP

25 5 Vol . 25, No. 5 2009 5 POL Y MER MAT ERIA LS SCIEN CE AN D EN GINEERIN G M ay 2009 O, O- 1, 2 1 1 1 1 李凤红 , 楚慧姝 , 王鲁霞 , 张 娜, 张宝砚 ( 1. , 110004; 2. , 111003 : 采用甲烷磺酸保护壳寡糖的氨基 , 通过月桂酰氯与壳寡糖的羟基反应合成了O , O- 双十二酰化壳寡糖 示扫描 量热( DSC 分析和热重分析( T GA 表明, 随着月桂酰氯与壳寡糖的摩尔比增加, O, O- 双十二酰化壳寡糖的 DSC 曲线出 现了月桂酰基侧链的熔融峰 , 而且 O, O- 双十二酰化壳寡糖的热稳定性均低于壳寡糖扫描电镜( SEM 及X 射线衍射 ( XRD 分析表明, 酰化反应改变了原壳寡糖的结晶结构, 并且月桂酰基侧链能够形成新的结晶微区溶解性实验结果表 明, 所有酰化壳寡糖在氯仿吡啶四氢呋喃中的溶解性得到改善 : ; ; ; ; : O636 . 1 : A : 1000- 7555( 2009 05- 0 139- 04 N- , O , O- , [ 1] ( CSO O , O- , ( , 1 [ 2] 1. 1 ( - N H2 ( - OH ( CSO : 3000, 80% , ; : , , [ 3, 4] ; : N- N , O [ 5~ 8] ; : , , [ 9] ; : , , Fig. 1 Synthetic procedure of O, O-dilauroyl chitosan oligosaccharide 1.2 O, O-(LCSO) 10 g ( 0. 5 mol 250 mL : 2008- 11-08 : 863 ( 863- 2006A A02Z 29 1 ; ( : , , E-mail: baoyanzhang@ hot mail. com 140 2009 , 20 mL , 4 h ~ 5 h , 10 Form ( 220 , , Form ( 212. 2 F orm ( 2 , 1 g 10 mL 25 ( F ig . 3b F ig . 3c , , , F orm ( 2 12 . 211. 2 , 3 h~ 4 h, , , Form ( 2 , , 25 F ig . 3c , O , O- / , ( 26 3, LCSO- 1 19. 72 1. 524 . 3, L CSO- 2O , O- , F ig. 1 , DSC 1.3 ( FT- IR PE Spect rum One ; XRD Xpert Pro MP D X , Cu K , 25~ 89, 1/ min; D SC N et zsch DSC 204 , 10 / min, ; T GA NET ZSCH T GA 209C , 10 / min, 30 ~ 400 , N2 ; , Fig. 2 F-IR spectra of (a) CSO, (b) LCSO-1 and (c) LCSO-2 SSX- 550 2 2. 1 O, O- F ig . 2 L CSO- 1 LCSO- 2 3000 cm- 1 ~ 3700 cm- 1 , 1640 cm- 1I , 1526 cm- 1 II N - H Fig. 3 X-ray diffraction diagrams of (a) CSO, (b) LCSO-1 and (c) LC- - 1 , LCSO- 1 LCSO- 2 3250 cm SO-2 , 1743 cm- 1 N ( COR 2 ( 17 16 cm- 1 , 1640 cm- 11526 cm- 1, 1028 cm- 1107 8 cm- 1 C- O , O, O- , , C- H ( 2962 cm- 1, 2924 cm- 1, 2853 cm- 1 ( 1467 cm- 1, 1412 cm- 1 , Fig. 4 DSCthermograms of (a) CSO, (b) LCSO-1 and (c) LCSO-2 2.3 O, O-(LCSO) 2.2 O, O-X F ig . 4Fig. 5 LCSO DSC F ig . 3 CSOLCSO- 1 LCSO- 2 X- ray T GA F ig . 4a , 84 , Form ( 2 5 : O, O- 14 1 , , X F ig . 4b , L CSO- 1 84 , , , , 43 F ig . 4c , O, O- , , 84 , 68 Fig. 5 , LCSO- 1 L CSO- 2 ( 205 , 179 17 8 , Fig. 5 GA thermograms of (a)CSO, (b) LCSO-1 and (c) LCSO-2 O , O- , Fig. 6 SEM micrographs of (a) CSO ( 4000) and (b) LCSO-2 ( 2000) 2.4 O, O- SEM O , O- , O , O- Fig . 6a F ig . 6b L CSO- 2 , SEM Fig . 6a , , , ( Fig. O , O- 6b , , , , LCSO , 2.5 : 50 mg L CSO- 1 LCSO- 2 [ 1] . [ M ] . : , 2003: 3- 4. 10 mL , 1 d [ 2] K IM S K , N IR ANJA N R . Enzymatic production and biological ac- , , L CSO t ivit ies of chit osan oligosaccharides ( COS : a review [ J] . Carbohy d. , P olym . , 2005, 62: 357- 368. L CSO- 1 ; L CSO- 2 [ 3] RA V IK U M A R M N V , M U ZZA REL LI R A A, M UZZ AR ELL I , , O, C, et al . Chit osan chemist ry and pharmaceut ical perspectives [ J ] . Chem . Rev . , 2004, 104 ( 12 : 60 17-6084. O- [ 4] J IA N G G B, Q U A N D P , LIA O K R , et al . Preparat ion of poly- meric micelles based on chit osan bearing a small amount of highly hy- 3 drophobic groups[ J] . Carbohy d. P olym . , 2006, 66: 5 14- 520. [ 5] BAD AWY M E I, R ABEA E I, RO GG E T M , et al . Synthesis an d fungicidal act ivit y of new N, O-acyl chitosan derivatives [ J ] . O , O- Biomacromol. , 2004, ( 5 : 589-595. , [ 6] Z ON G Z , K IM U RA Y , T AK AHA SHI M , et al . C haract erizat ion FT- IR DSCT GAX SEM of chem ical and solid st at e st ruct ures of acylat ed chitosans[ J ] . P oly- 142 2009 mer, 2000, 4 1: 899- 906. , 2008, 24 ( 2 : 152- 158. [ 7] SA SHIWA H, KA WA SAK I N , NA KA Y AM A A , et al. Chemical WAN G J T , CHA NG D F . Preparat ion and characterization of p- modification of chitosan 13: synt hesis of organosoluble, palladium ad- benzoylaminobenzoyl chitosan [ J ] . Polym . M at er . Sci. Eng . , sorbable, and biodegradable chit osan derivat ives tow ard the chemical 2008, 24 ( 2 : 152- 158. plat ing on plastics[ J] . Biomacromol. , 2002, 3( 5 : 1120- 1125. [ 9] K U M A R M . A review of chit in and chit osan applicat ions[J ] . React . [ 8] , . [ J] . Funct . P olym . , 2000, 46: 1- 27. Solubility and Solid Structure of O, O-Dilauroyl Chitosan Oligosaccharide 1, 2 1 1 1 1 LI Feng-hong , CHU Hu-i shu , WA N G Lu-xia , ZHA N G N a , ZHA N G Bao-yan ( 1. Centerf or Molecular Science and Engineering, Northeastern University, Shenyang 110004, China; 2. School of etrochemical Engineering, Shenyang University of Technology, L iaoyang 111003, China) ABS RAC :O, O- dilauroyl chitosan oligosaccharide ( L CSO w as synt hesized by t he react ion of the hy drox yl g roup of chit osan oligosaccharide ( CSO and suit able count of lauroyl chloride via the amino groups prot ection procedure w it h met hane sulfonic acid. Dif ferent ial scanning calorimet ry ( DSC and thermogravimetric analyse ( T GA show s that melting endot hermal peak of lauroyl side chains occurs in DSC curve of L CSO w ith the increasing of the mole ra- t io of lauroyl chloride to CSO , besides, all the LCSO has less t hermal st ability than orig inal CSO . Scanning elect ron microscope ( SEM and X- ray dif fract ion ( X RD analyses indicate t hat t he orig inal crystal structure of CSO does change w it h the lauroyl acylat ions and has created new crystal domain of lauroyl side chains. T he experiment al result s of solubilit y show t hat the solubilit y of all the acylat ed chit osan oligosaccharides has been improved in chloroform, pyridine and t et rahydrofuran. Keywords:chitosan oligosaccharide; acylat ion ; solubilit y; solid struct ure; charact erizat ion ( 138 continued f rom p. 138 Effects of Gamma-Ray Irradiation on Surface Charge Accumulation on PolybutyleneNaphthalate 1 1 1, 2 DU Bo-x ue , GAO Y u , ZH U X iao- hui (1. School of Electrical Engineering A utomation, Tianj in University, Tianj in 300072, China; 2. Tianj in Electrical ower Science Research Institute, Tianj in 300040, China) ABS RAC :In this paper, polybut ylene naphthalate ( PBN was employed as t est sample to investigat e the ef fects of g amm a- ray irradiation on surface charge accumulat ion. T he sample w as previously irradiat ed in air up t o 100 kGy and 60 then u