采用酶促法合成含半乳糖单体6-O-乙烯基壬二酸-D-吡喃型半乳糖酯(OVZG),采用可逆加成-链断裂转移自由基聚合法(RAFT聚合)将大分子引发剂二聚乙二醇单甲醚甲基丙烯酸甲酯(DEGMA)和 OVZG有效结合,制备相对分子质量(简称分子量)分散系数(PDI)较低的温敏性含半乳糖嵌段共聚物PDEGMA-b-POVZG.通过核磁共振氢谱(1 H NMR),傅里叶变换红外光谱(FT-IR),凝胶渗透色谱(GPC)对聚合物结构进行了确认表征.通过紫外-可见光谱(UV-Vis)研究表明,共聚物的低临界溶解温度(LCST)可以通过共聚单体的比例进行调控,当PDEGMA与OVZG的物质的量之比为1∶63时,含糖共聚物的LCST值为33℃.在37℃生理温度下,PDEGMA-b-POVZG可以自组装形成纳米胶束,透射电子显微镜(TEM)显示自组装形成的聚合物胶束是结构均匀、形貌规整的球形,通过动态光散射(DLS)测得纳米微球的粒径约为167 nm,该温敏性半乳糖嵌段共聚物在药物载体方面具有潜在的应用前景.
The glycomonomer 6-O-vinylazelaic-D-galactopyranose (OVZG)was synthesized by lipase catalyzed transesterification of divinyladipate with D-galactopyranose.PDEGMA-b-POVZG with narrow polydispersity (PDI)and obvious thermosensitivity was effectively prepared via enzymatic synthesis combined with reversible addition-fragmentation chain transfer (RAFT)polymerization.The structure and molecular weight of the syn-thesized glycopolymer were characterized by 1 HNMR,FT-IR and gel permeation chromatography (GPC),re-spectively.Measurement by dynamic light scattering (DLS)and transmission electron microscopy (TEM)re-vealed that PDEGMA-b-POVZG was able to self-assemble into nano-micelles with well-defined structure and u-niform size in aqueous solution.UV-Visible spectroscopy tests showed that the low critical solution temperature (LSCT)of the polymer can be controlled by the molar ratio of monomers.Especially,as the molar ratio of PDEGMA and OVZG was 1∶63,the LCST of PDEGMA-b-POVZG could be 33 ℃ in aqueous solution.The re-sults demonstrate that PDEGMA-b-POVZG can form nano-micelles in the human body environments,which may have potential as functional drug carriers.
参考文献
| [1] | Andrew B.Lowe;Brent S.Sumerlin;Charles L.McCormick.The direct polymerization of 2-methacryloxyethyl glucoside via aqueous reversible addition-fragmentation chain transfer (RAFT) polymerization[J].Polymer: The International Journal for the Science and Technology of Polymers,200322(22):6761-6765. |
| [2] | Hua Wei;Si-Xue Cheng;Xian-Zheng Zhang.Thermo-sensitive polymeric micelles based on poly(N-isopropylacrylamide) as drug carriers[J].Progress in Polymer Science,20099(9):893-910. |
| [3] | Wang, Y.;Li, X.;Hong, C.;Pan, C..Synthesis and micellization of thermoresponsive galactose-based diblock copolymers[J].Journal of Polymer Science, Part A. Polymer Chemistry,201115(15):3280-3290. |
| [4] | Ozyurek Z;Komber H;Gramm S;Schmaljohann D;Muller AHE;Voit B.Thermoresponsive glycopolymers via controlled radical polymerization[J].Macromolecular chemistry and physics,200710(10):1035-1049. |
| [5] | Hoshino, Y.;Nakamoto, M.;Miura, Y..Control of protein-binding kinetics on synthetic polymer nanoparticles by tuning flexibility and inducing conformation changes of polymer chains[J].Journal of the American Chemical Society,201237(37):15209-15212. |
| [6] | 田静;万灵书;徐志康.含糖聚合物可控合成研究进展[J].化学通报（印刷版）,2008(2):102-109. |
| [7] | Wu, C.;Xie, J.;Branford-White, C.;Quan, J.;Zhu, L..In vitro controlled release of polymeric drug-saccharide conjugates with ketoprofen, ibuprofen, and naproxen pendants[J].Journal of Applied Polymer Science,20113(3):1654-1660. |
| [8] | Quan J;Wu O;Zhu LM;Lin XF.Chemo-enzymatic synthesis and sustained release of optically active polymeric prodrugs of chlorphenesin[J].Polymer: The International Journal for the Science and Technology of Polymers,200816(16):3444-3449. |
| [9] | Dupayage L;Save M;Dellacherie E;Nouvel C;Six JL.PMMA-Grafted Dextran Glycopolymers by Atom Transfer Radical Polymerization[J].Journal of Polymer Science, Part A. Polymer Chemistry,200823(23):7606-7620. |
| [10] | Wang, Z.H.;Li, W.B.;Ma, J.;Tang, G.P.;Yang, W.T.;Xu, F.J..Functionalized nonionic dextran backbones by atom transfer radical polymerization for efficient gene delivery[J].Macromolecules,20112(2):230-239. |
| [11] | Luca Albertin;Claudia Kohlert;Martina Stenzel;L.John R.Foster;Thomas P.Davis.Chemoenzymatic Synthesis of Narrow-Polydispersity Glycopolymers: Poly(6-O-vinyladipoyl-D-glucopyranose)[J].Biomacromolecules,20042(2):255-260. |
| [12] | Lou, S.-F.;Zhang, H.;Williams, G.R.;Branford-White, C.;Nie, H.-L.;Quan, J.;Zhu, L.-M..Fabrication and aggregation of thermoresponsive glucose-functionalized double hydrophilic copolymers[J].Colloids and Surfaces, B. Biointerfaces,2013:180-186. |
| [13] | 刘丽;石海婷;王晓蓓;吕文慧;罗燕.功能性含糖聚合物的研究[J].高分子通报,2013(1):167-173. |
- 下载量()
- 访问量()
- 您的评分：
-
10%
-
20%
-
30%
-
40%
-
50%