蔗糖基聚合物的预辐射法和酶法合成及其应用研究
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摘要
含糖聚合物是指通过不同的反应途径把糖组分引入到聚合物分子链中而形成的高分子聚合物。蔗糖基聚合物(Sucrose-based polymer,SBP)就是其中之一。本文采用一种新的方法——预辐射法合成蔗糖基聚合物,即蔗糖在~(60)C_o的γ射线辐照下变成了具有引发活性的活化蔗糖,离开辐射场后再和另一种单体发生聚合反应,从而生成蔗糖基聚合物。同时对蔗糖基聚合物的有机相酶催化合成法进行了初步研究。
     在预辐照法中,研究了反应单体、蔗糖预辐射剂量、存放时间、温度、反应物料配比对蔗糖基聚合物的粘均相对分子量和产率的影响。研究表明,要获得适合于农业生产应用的蔗糖基聚合物,其相对分子量为6万左右,蔗糖和单体的最优聚合反应条件为:预辐射剂量1kGy、反应温度为常温20℃;反应时间15h;水、蔗糖与单体配比为5:5:1(v/w/v)。
     有机相酶催化法研究表明,Novozmy-435催化己二酸二乙烯酯与蔗糖反应中具有很高的选择性,己二酸二乙烯酯主要和蔗糖的C-6和C-6′反应生成蔗糖二酯。
     本文对预辐射法合成的蔗糖基聚合物在药物缓释、水果保鲜和植物生长调节剂等方面的应用进行了研究。结果表明,蔗糖基聚合物对药物缓释有较好的效果,缓释时间可达12小时左右。蔗糖基聚合物制备非诺洛芬钙缓释片的最佳实验条件是:非诺洛芬钙、蔗糖基聚合物、海藻酸钠的质量配比为1:5:3。蔗糖基聚合物作为水果保鲜剂,可以保持水果品质,有较明
Sugar-containing polymers mean that through different responses to lead to sugar polymer molecular chain group and to form macromolecular polymers. Sucrose-based polymer (SBP) is the one of them. This dissertation focuses on a new method to synthesize sucrose-based polymer (SBP) — pre-irradiation method. Sucrose crystal was pre-irradiated by γ-ray of ~(60)Co and turned into an activated form, then the activated sucrose was polymerizes directly with another monomer (e.g. acrylic acid) to yield SBP.Preliminary study on enzymatic synthesis of polymerisable vinyl sugar esters in non-aqueous media and preparation of polymers containing sugar branches.
    The effects of different monomers, pre-irradiation dose, store days of pre-irradiation sucrose, reaction temperature, monomer concentration ratio to the relative molecular weight and yield of the polymers were studied. The results
引文
[1] 孟建文,谭业邦,王成威.含糖聚合物的合成[J].高分子通报,2002(5):66-72
    [2] Gardner D R, Sanders R A. Isolation and characterization of polymers in heated olestra and an olestra/triglyceride blend[J]. Journal of the American Oil Chemical Society, 1990, 67,788-796
    [3] Hough L. Applications of the chemistry of sucrose[M]. In F. W. Lichtenthaler (Ed.), Carbohydrates as Organic Raw Materials, 1991, New York: VCH chap. 2
    [4] Schiweek H, Munir M, Rapp K M. New development in the use of sucrose as an industrial bulk chemical[M]. In F. W. Lichtenthaler (Ed.), Carbohydrates as Organic Raw Materials, 1991, New York: VCH chap. 3
    [5] Marcy W. Licensing programs for sucrochemical inventions[J]. ACS Symposium Series,1977,41,328-335
    [6] Chen X, Dordick J S, Rethwisch D G. Chemoenzymatic synthesis and characterization of poly(α-methyl galactoside 6-actylate) hydrogels[J]. Macromolecules, 1995,28,6014-6019
    [7] Patil N S, Dordick J S, Rethwisch D G. Macroporous poly(sucrose acrylate) hydrogel for controlles release of macromolecules[J]. Biomaterials, 1996, 17:2343-2350
    [8] Chen J, Park K. Synthesis of fast-swelling, superporous sucrose hydrogels[J]. Carbohydrate Polymers, 2000,41,259-268
    [9] Fanton E, Fayel C. Synthesis of 4-O-and 6-O-monoacryloyl derivatives of sucrose by selective hydrolysis of 4,6-O-(1-ethoxy-2-propenylidene) sucrose. Polymerization and copolymerization with styrene[J]. Carbohydrate Research, 1993,240:143-152
    [10] Kunz M. From sucrose to semisynthetical polymers[J]. In G. Descostes (Ed.), Carbohydrates as organic raw materials, 1993:135
    [11] Kazuhiko H, Ryo O.Glycopolymeric Inhibitors of β-Glucuronidase. Ⅰ .Synthesis and Polymerization of Styrene Derivatives Having Pendant D-Glucaric Moieties[J]. Journal of Polymer Science Part A: Polymer Chemistry, 1999,37(3):303-312
    [12] Kazuhiko H, Ryo O.Glycopolymeric Inhibitors of β-Glucuronidase. Ⅱ. Synthesis of Glycopolymers Containing Pendant L-Gulonic Moieties and Effects the Carboxyl Group in the Clycopolymers upon the Activity of β-Glucuronidase[J]. Journal of Polymer Science Part A: Polymer Chemistry, 1999,37(15):2773-2779
    [13] Wen Z, Mark J K.Synthesis and Thermal Properties of a Novel Lactose Containing Poty(N-isopropylacrylamide-co-acrylamidolactamine)Hydrogel[J]. Journal of Polymer Science Part A: Polymer Chemistry, 1999,37(10): 1393-1402
    [14] Wilson M, Najdi S, Kurth M.Complexation of Borate with Poly(1-(acrylamido)-1-deoxylactitol): Dilute Solution Viscosity, ~(11)B NMR, and ~(13)C NMR Studies [J].Macromolecules, 1998,31 (14):4486-4492
    [15] Kohji O, Yoshinobu T.Synthesis of a Well-Defined Glycopolymer by Atom Transfer Radical Polymerization[J]. Journal of Polymer Science Part A: Polymer Chemistry, 1998,36(14):2473-2481.
    [16] Goto A, Ohno K, Fukuda T.Mechanism and kinetics of iodide-mediated polymerization of styrene [J].Macromolec, 1998, 31: 2809-2814
    [17] Kitagawa M, Yakegami S, Tokiwa Y. Enzymatic synthesis of vinyl uridine esters catalyzed by Bioprase, alkaline protease from Bacillus subtilis[J]. Biochemical Engineering Journal.2004, 21(3): 279-28
    [18] Grande D, Baskaran S.Glycosamionglycan-mimetic Biomaterials.1. Nonsulfated and sulfated Glycopolymers by Cyanoxyl-Mediated Free-Radical Polymerizatio[J].Macromolecules, 2000,33,1123-1125
    [19] Grande D, Baskaran S. Glycosaminoglycan Mimetic Biomaterials. 2. Alkene- and Acrylate-Derivatized Glycopolymers via Cyanoxyl-Mediated Free-Radical Polymerization[J]. Macromolecules,2001,34(6): 1640-1646
    [20] Martin B. Biocatalytic synthesis of sugar-containing polyacrylate-based hydrogels [J].Macromolecules, 1992,25(26):7081-7085
    [21] Chen X M, Dordick J S, Rethwidch D G. Chemoenzymic Synthesis and Characterization of Poly(.alpha.-methyl galactoside 6-acrylate) Hydrogels[J].Macromolecules, 1995,28(18):6014-6019.
    [22] DordickJ S. Sugar acrylate-based polymers as chiral molecularly imprintable hydrogels[J]. Journal of Polymer Science:PartA :Polymer Chemistry, 1999,37(11): 1665-1671
    [23] Patil R, Dordick S, Rethwisch G. Chemoenzymatic synthesis of novel sucrose-containing polymers [J]. Macromolecules, 1991,24(11):3462-3463
    [24] Higashimura T, Aoshima S, Sawamoto M. New initiators for living cationic polymerization of vinyl compound[J]. Makromol Chem, Macromol Symp, 1988, (13):457~471
    [25] Yamada K, Minoda M.Controlled Synthesis of Amphiphilic Block Copolymers with Pendant N-Acetyl-D-glucosamine Residues by Living Cationic Polymerization and Their Interaction with WGA Lectin [J].Macromolecules 1999,32,3553
    [26] Nakahama S, Hirao A.Protection and polymerization of functional monomersanionic living polymerization of protected monomers [J],Prog.Poly.Sci. 1990,15,299
    [27] Loykulnant S, Hayashi M.Protection and Polymerization of Functional Monomer: 28.Anionic Living Polymerization of Styrene Derivatives Containing Acetal-Protected Monosaccharide Residues [J],Macromolecules 1998,31,9121
    [28] Janssen A, Riet K. Enzymatic synthesis of carbohydrate esters in aqueous media[J]. Biotechnology Letters, 1990, 12,711-716
    
    [29] Pitt C. The controlled parenteral delivery of polypeptides and proteins[J]. Int. J. Pharm. 1990, 59:173
    [30] Atkins T W. Low temperature incorporation of bovine serum albumin into a bead formes macroporous hydrophilic polymer matrix with potential for sustained release[J]. J. Biomater Sci., Polym. Edn., 1992,3:261
    [31] Peppas N A, Scott J E. Controlled release from poly(vinyl alcohol) gels prepared by freezing-thawing processes[J]. J. Contr. Rel., 1992, 18:95
    [32] Atkins T W, McCallion R L. The incorporation and sustained release of bioactive insulin form a bead-formed macroporous hydrogel matrix[J]. J Biomed Mater Res 1995, 29:291
    [33] Ficek B J, Peppas N A. Novel preparation of poly(vinyl alcohol) microparticles without crosslinking agent for controlled drug delivery of proteins[J]. J Biomed Mater Res 1993, 27:259
    [34] Dong L. Yan Q. Controlled release of amylase from a thermal and pH-sensitive, macroporous hydrogel[J]. J Contr Rel 1992, 19:171
    
    [35] Davis B K. Diffusion in polymer gel implants [J]. Proc Natl Acad Sci USA 1974, 71:3120
    [36] Dordick J S, Linhardt R L, Rethwisch, D G..Chemical and biochemical catalysis to make swellable polymers [J]. Chemtech 1994, 24:33
    [37] Patil N S, Dordick J S, Rethwisch, D GMacroporous poly(sucrose acrylate) hydrogel for controlles release of macromolecules[J]. Biomaterials, 1996, 17:2343-2350
    
    [38] Nickell LG Plant growth regulator. Hedin PA [C]. Proc 18~(th) Ann Mtg. Soc. Amer.New York, 1991
    [39] Bandara P, Tanino K. Paclobutrazol enhances mini tuber production in Norland potatoes [J]. Plant growth regulator, 1995, 14:151-155
    [40] 王熹,陶龙兴.大田作物化控技术研究进展与应用前景[J].中国农业科技报,2000,2(2):55-57
    [41] 王熹,俞美玉,陶龙兴,等.作物化控原理[M].北京:中国农业科技出版社,1997
    [42] Brenner M. The role of hormones in photosysthate parting and seed filling[A]. Davis P J. Plant Hormones and Their Role in Growth and Development[C].Martinus Nijihoff ublishers, 1987,473-479
    [43] Zeffari G R, Peres P, Kerbauy G B. Endogenous levels of cytokinins, Indoleacetic acid, Abscisic acid, and Pigments in variegated soma clones of micro propagated banana leaves[J]. Plant Growth Regulator, 1998, 17(2):59-61
    [44] Mazzei R O, Smolko E. Radiation grafting studies of acrylic acid onto cellulose triacetate membranes[J]. Radiation Physics and Chemistry, 2002, 64:149-160
    [45] 哈鸿飞,吴季兰.高分子辐射化学——原理与应用[M].北京:北京大学出版社,2002:27
    [46] 张志成,葛学武,张曼维.高分子辐射化学[M].合肥:中国科学技术大学出版社,2000:66
    [47] 包华影,贾海顺,曲国翠等.~(60)Coγ射线预辐照制备淀粉-丙烯酰胺接枝物[J].辐射研究与辐射工艺学报,2000,18(4):263-267
    [48] 谭绍早,李光吉,沈家瑞,等.PP无纺布预辐射接枝4-乙烯基吡啶的研究[J].高分子材料科学与工程,2000,16(3):142-144
    [49] 钱群,吴明红,包伯荣.丙烯酰胺在预辐照聚丙烯纤维上接枝反应的研究[J].辐射研究与辐射工艺学报,2001,19(4):259-262
    [50] Chen J, Yang L. Preparation of interpenetrating polymer networks by two times grafting of monomers onto preirradiated polypropylene film. Radiation Phys[J]. Chem. 59(2000), 313-316.
    [51] Chen J.Studies on preparation of biomedical hydrogels by radiation cross linking and graft copolymerization[D]. PhD thesis of Kinki University, 2001
    [52] Katano H, Sanui K. Drug release off behavior and deswelling kinetics of thermo-responsive IPNs composed of poly(acrylamide-co-butylmethacrylate) and poly(acrylic acid)[J]. Polymer Journal, 1991, 23(10), 1179-1189
    [53] 王久芬.高分子化学[M].哈尔滨工业大学出版社,2004:83
    [54] 张宇东,陈代涛,施鼐.PP预辐射接枝丙烯酸酯的研究[M].高分子材料科学与工程,1999,15(5):79-82
    [55] 张清林,张宝军.驱油用高相对分子量聚丙烯酰胺的制[M].化学工业与工程,1999,16(5):300-304
    [56] Li J, Zhai M.Radiation Physics and Chemistry[M].1999:173
    [57] 陈代涛,谢立青,周维金,等.电子束预辐照聚丙烯与丙烯酸的接枝共聚物[J].高分子学报,2000,1(2):32-35
    [58] Arcos J A., Bernabe M, Otero C. Quantitative enzymatic production of 1,6-diacyl fructofuranoses[J]. Biotechnology and Bioengineering, 1998, 60(1): 53-60
    [59] Sarney D B, Vulfson E N. Application of enzymes to the synthesis of surfactants[J].Trends Biotechnology, 1995,13(5): 164-172
    [60] 铁翠娟,寇秀芬,徐家立.固定化脂肪酶催化合成6,6'-海藻糖月桂酸酯[J].催化学报,2002,23(1):81-84
    [61] Guillemard E, Geniteau M. Role of trehalose dimycolate-induced interferon-α/β in the restriction of encephalomyocarditis virus growth in vivo and in peritoneal macrophage cultures[J]. Mabboux,Antiviral Res., 1993,22:201
    [62] Ducret A,Giroux A.Bipolar electrolysis for tritium recovery from weakly active tritiated water [J].Biotechnology and Bioen gineering, 1995,48(3):214-221
    [63] Vulfson E. Application of enzymes to the synthesis of surfactants[J]. Food Set.Technol, 1993,4:209.
    [64] 罗贵民.酶工程[M].化学工业出版社,2002
    [65] Klibanov A. Why are enzymes less active in organic solvents than in water[J].Chemtech 1986,16,354
    [66] Russel A J, Klibanov A M. Asymmetric enzymatic oxidoreductions in organic solvents[J]. Current Opinion in Biotechnology. 2003,14(4) : 427-431
    [67] Zaks A, Klibanov A M. Organic Solvent Binding to Crystalline Subtilisin~1 in Mostly Aqueous Media and in the Neat Solvents[J]. Biochemical and Biophysical Research Communications 1998, 248(2): 273-277
    [68] Therisod M, Klibanov A M.Facile enzymatic preparation of monoacylated sugars in pyridine[J]. Am.Chem.Soc., 1986,108(18):5638-5641
    [69] Therisod M, Klibanov A.A novel progesterone-induced messenger RNA in rabbit and human endometria. Cloning and sequence analysis of the complementary DNA[J]. Am.Chem.Soc, 1987,109(26):3977-3982
    [70] 吴起.非水介质酶促方法与含糖化合物合成研究[D].浙江大学博士学位论文,2003,11
    [71] Carrea G, Riva S, Secundo F. A chemoenzymatic approach to the synthesis of the stereoisomers of a β-adrenergic receptor antagonist[J]. 2000, 11 (13): 2741-2751
    [72] Francesco S, Giacomo C. Lipase activity and conformation in neat organic solvents[J]. Journal of Molecular Catalysis B:Enzymatic,2002,19,93-102
    [73] 李延科,张淑芬,杨锦宗.蔗糖酯的酶催化区域选择性合成[J].有机化学,2003,23(8):770-775
    [74] Rob S, Kieboom T. Combined catalytic conversion involving an enzyme, a homogeneous and a heterogeneous catalyst: one-pot preparation of 4-deoxy-d-glucose derivatives from d-galactose[J]. Tetrahedron Letters ,2002,43(18):3399-3400
    [75] Pezzotti F, Therisod M.Enzymatic synthesis of d-glucosaminic acid from d-glucosamine[J]. Carbohydrate Research, 2005, 340(1):139-141
    [76] Rich J O, Bedell B A, Dordick J S. Enzyme activation for nonaqueous media[J].Biotechnol Bioeng, 1995,45:42
    [77] 纪立伟.药物制剂与控制制剂[J].中国临床医生,2005,33(6):39
    [78] 朱兴安.药物缓释、控制制剂的研究进展[J].药学实践杂志,2000,20(3):155-157
    [79] 刘晨光,刘成圣,孟详红,等.壳聚糖作为药物缓材料的研究进展[J].科技通讯,2003,3:88
    [80] 苑振亭,王晓文,赵中华,等.氢溴酸右美沙芬缓释片的制备及释放度研究[J].中国医院药学杂志1999,19(10):5981
    [81] 要芬梅,冯超英,蔡长春,等.新型依托泊苷胶囊的研制及释放度研究[J].中国药房,1999,19(3):1061
    [82] 崔一民,鲁云兰.利福平白蛋白微球的研制[J].中国医院药学杂志,1999,19(3):1311
    [83] 张静,平其能.口服择时释药系统[J].药学进展,1999,23(5):2651
    [84] 张光曙.非诺洛芬治疗227例关节炎患者的临床观察[J].新药与临床,1986,5(3):129
    [85] 董金陵.苯氧布洛芬钙[J].医药工业,1985,16(8):46
    [86] 陈龙美,叶武军,秦至龙.盐酸环丙沙星溶出度的考察[J].中国药事,1996,10(6):405-406
    [87] 蒋挺大.壳聚糖[M].北京:化学工业出版社,2001.12;160-203
    [88] 中华人民共和国卫生部药典委员会编.中华人民共和国药典:一九九五年版(二部)[M].北京:化学工业出版社,1995.114;附录68;附录177;506
    [89] Sugibayashi K, Akimkoto M.Drug cartier property on albumin micropheres entrapped 5-fluorouracil on ehrlich ascites carcinoma in mice[J]. Pharmacobiodyn, 1979,(2):350-354
    [90] Hari P R,Thomas C.PS Chitosan/calciumaiginate beads for oral delivery of insulin [J].J.AppL.Poly.Sci, 1996,59:1795-1801
    [91] 彭湘红,杜金平,王敏娟,等.甲基丙烯酸与壳聚糖接枝共聚物的制备及应用研究[J].精细化工,2000,17(3):137-139
    [92] 陈文.我国果蔬保鲜技术发展近况[J].贮藏加工,1999,24
    [93] 罗先群.新型芒果保鲜剂的保鲜试验[J].食品科学,1996,(6):61-63
    [94] 苏小军,蒋跃明,于新,等.芒果采后生物学及贮运保鲜技术研究进展[J].仲恺农业技术学报,2001,14(1):16-66
    [95] 季作梁,张昭其.芒果低温贮藏及其冷害的研究[J].园艺学报,1994,(2)
    [96] 朱德明,陈民,李珠柱.芒果保鲜系统剖析[J].广西热带农业,2001(2):9-11
    [97] 罗先群.新型芒果保鲜剂的保鲜试验[J].食品科学,1996(6):61-63
    [98] 谢艺贤,杨业铜,张开云,等.芒果贮藏保鲜效果的检测分析 [J].华南热带农业大学学报,1999,5(3):5-9
    [99] 蔡武城.生物物质常用化学分析法[M].科学出版社,1982:36
    [100] 奚长生.磷钼蓝分光光度法测定维生素C[J].光谱学与光谱分析,2001,(5):723-725
    [101] 荣瑞芬,佟世生,冯双庆.水杨酸对采后芒果和番茄保鲜效果的初步研究[J].食品科学,2001,22(1):79-81
    [102] 覃志英,盛家荣,陈超球,等.壳聚糖常温保鲜芒果的试验[J].广西化工,1999,28(1):23-25
    [103] 赵玉梅,冯双庆.保鲜剂在芒果储藏保鲜中的应用试验[J].山西果树,2001,83(1):29-30
    [104] 陆晓民.植物生长调节剂在平菇栽培中的应用研究[J].中国林副特产,2001,56(1):19-20
    [105] 李勇,田力嘉.猴头菇玉米粒菌种培养基与高产配方研究[J].中国食用菌,2003,22(1):23-24
    [106] 莫天砚.食用药用菌栽培技术[M].北京:中国农业大学出版社2003.1
    [107] 杨缙湘.食用菌栽培原理与技术[M].长沙:湖南科学技术出版社1992
    [108] 李仲芳,陈坤明,张占甲.激素与营养液配施对平菇产量及品质的影响[J].食用菌学报,1995,2(2):33-37
    [109] 蒋冬花,张萍华.植物生长调节剂对平菇菌丝生长和产量的影响[J].浙江师大学报(自然科学版),1996,19(4):86-89

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