基于β-环糊精的有机小分子凝胶
|
摘要
环糊精是直链淀粉在环糊精葡萄糖基转移酶作用下生成的含有7个D-吡喃葡萄糖单元的环状低聚糖,具有斜截锥形空间立体结构,腔内疏水,腔外亲水。β-环糊精以其低廉的价格、良好的水溶性和生物相容性,在超分子化学领域得到广泛的应用。β-环糊精可用于凝胶的构筑,通常的方法是将β-环糊精接枝到高分子链上,再以得到的高分子链为凝胶因子构筑高分子凝胶。虽然基于β-环糊精的高分子凝胶得到了广泛的关注和研究,但是,直接以β-环糊精为凝胶因子构筑的有机小分子凝胶却鲜有报道。2010年,本课题组首次报道了一种基于β-环糊精和二苯胺的热致有机凝胶。此后,本课题组在β-环糊精有机小分子凝胶领域做了大量的研究工作。本文在实验室研究工作的基础上,首先介绍了β-环糊精有机小分子凝胶的分类和不同因素对凝胶形成的影响,然后深入探讨了β-环糊精有机小分子凝胶的形成机理,系统介绍了β-环糊精有机小分子凝胶的刺激响应性以及在药物载运领域的应用,最后,对β-环糊精有机小分子凝胶的发展前景进行了展望。
β-cyclodextrin is a cyclic oligosaccharide containing seven glucopyranose units,and can be produced by amylose under the action of cyclodextrin glucosyltransferase. β-cyclodextrin has cone shaped threedimensional structure,with its cavity hydrophobic,while its outside hydrophilic. β-cyclodextrin has already been used widely in supramolecular chemistry due to its lowprice, good solubility and biocompatibility. β-cyclodextrin can be used to construct gel. But the usual way is grafting β-cyclodextrin onto polymer chain,and the obtained polymer chain containing β-cyclodextrin can act as gelator to construct polymer gel. Although polymer gels based on β-cyclodextrin have been studied extensively,there are fewreports about lowmolecular weight organogel based on β-cyclodextrin. In 2010,our lab reported heat-set lowmolecular weight organogel based on β-cyclodextrin and diphenylamine for the first time. After that,a lot of research work about lowmolecular weight β-cyclodextrin organogel has been done in our group. Based on the research foundation of our lab,in this review,classification of different lowmolecular weight β-cyclodextrin organogel and different factors affecting the formation of lowmolecular weight β-cyclodextrin organogel are introduced at first. Then,the formation mechanism of lowmolecular weight β-cyclodextrin organogel is discussed deeply, and stimuli responsiveness of lowmolecular weight β-cyclodextrin organogel and application of lowmolecular weight β-cyclodextrin organogel on drug delivery are introduced systematically. Finally,development foreground of lowmolecular weight β-cyclodextrin organogel is prospected.
β-cyclodextrin is a cyclic oligosaccharide containing seven glucopyranose units,and can be produced by amylose under the action of cyclodextrin glucosyltransferase. β-cyclodextrin has cone shaped threedimensional structure,with its cavity hydrophobic,while its outside hydrophilic. β-cyclodextrin has already been used widely in supramolecular chemistry due to its lowprice, good solubility and biocompatibility. β-cyclodextrin can be used to construct gel. But the usual way is grafting β-cyclodextrin onto polymer chain,and the obtained polymer chain containing β-cyclodextrin can act as gelator to construct polymer gel. Although polymer gels based on β-cyclodextrin have been studied extensively,there are fewreports about lowmolecular weight organogel based on β-cyclodextrin. In 2010,our lab reported heat-set lowmolecular weight organogel based on β-cyclodextrin and diphenylamine for the first time. After that,a lot of research work about lowmolecular weight β-cyclodextrin organogel has been done in our group. Based on the research foundation of our lab,in this review,classification of different lowmolecular weight β-cyclodextrin organogel and different factors affecting the formation of lowmolecular weight β-cyclodextrin organogel are introduced at first. Then,the formation mechanism of lowmolecular weight β-cyclodextrin organogel is discussed deeply, and stimuli responsiveness of lowmolecular weight β-cyclodextrin organogel and application of lowmolecular weight β-cyclodextrin organogel on drug delivery are introduced systematically. Finally,development foreground of lowmolecular weight β-cyclodextrin organogel is prospected.
引文
[1] Shen Z C,Wang T Y,Liu M H. Angew. Chem. Int. Ed.,2014,53:1.
[2] Hisamatsu Y, Banerjee S, Avinash M B, Govindaraju T,Schmuck T. Angew. Chem. Int. Ed.,2013,52:12550.
[3] Tam A Y,Wong K M,Yam V W. Chem. Eur. J.,2009,15:4775.
[4] Ma M F,Gu J G,Yang M M,Li Z L,Lu Z Q,Zhang Y M,Xing P Y,Li S Y,Chu X X,Wang Y J,Li Q,Lin M Y,Hao A Y. RSC Adv.,2015,5:70178.
[5] Xing P Y, Chu X X, Li S Y, Ma M F, Hao A Y.ChemPhysChem,2014,15:2377.
[6] Xing P Y,Chu X X,Ma M F,Li S Y,Hao A Y. Chem. Asian J.,2014,9:3440.
[7] Sui J F,Wang L H,Zhao W R,Hao J C. Chem. Commun.,2016,52:6993.
[8] Song S S,Feng L,Song A X,Hao J C. J. Phys. Chem. B,2012,116:12850.
[9] Nanda J,Biswas A,Adhikari B,Banerjee A. Angew. Chem. Int.Ed.,2013,52:5041.
[10]童林荟(Tong L H).环糊精化学———基础与应用(Cyclodextrin Chemistry———Foundation and Application).北京:科学出版社(Beijing:Science Press),2001. 10.
[11] Sun T,Li Y M,Zhang H C,Li J Y,Xin F F,Kong L,Hao A Y. Colloids Surf. A,2011,375:87.
[12] Sun T,Guo Q,Zhang C,Hao J C,Xing P Y,Li S Y,Hao A Y,Liu G C. Langmuir,2012,28:8625.
[13] Sun T,Zhang H C,Kong L,Qiao H W,Li Y M,Xin F F,Hao A Y. Carbohydra. Res.,2011,346:285.
[14] Ma M F,Su J,Sheng X,Su F,Li S Y,Xing P Y,Hao A Y. J.Mol. Liq.,2014,198:1.
[15] Zhou C C,Cheng X H,Zhao Q,Yan Y,Wang J D,Huang J B.Scientific Reports,2014,4:7355.
[16] Zhou C C,Huang J B,Yan Y. Soft Matter,2016,12:1579.
[17] Chen L,Chen H,Yao X Y,Ma X,Tian H. Chem-Asian J.,2015,10:2352.
[18] Chen H,Ma X,Wu S F,Tian H. Angew. Chem.,2014,126:14373.
[19] Zhang Q W,Qu D H,Wu J C,Ma X,Wang Q C,Tian H.Langmuir,2013,29:5345.
[20] Nakahata M,Takashima Y,Harada A. Angew. Chem. Int. Ed.,2014,53:3617.
[21] Miyamae K,Nakahata M,Takashima Y,Harada A. Angew.Chem. Int. Ed.,2015,54:8984.
[22] Kakuta T,Takashima Y,Sano T,Nakamura T,Kobayashi Y,Yamaguchi H,Harada A. Macromolecules,2015,48:732.
[23] Nakahata M,Takashima Y,Harada A. Macromol. Rapid Comm.,2015,37:86.
[24] Zheng Y T,Kobayashi Y,Sekine T,Takashima Y,Hashidzume A,Yamaguchi H, Harada A. Nat. Commun., 2018, DOI:10. 1038/s42004-017-0003-x.
[25] Takashima Y,Sawa Y,Iwaso K,Nakahata M,Yamaguchi H,Harada A. Macromolecules,2017,50:3254.
[26] Koyanagi K, Takashima Y, Yamaguchi H, Harada A.Macromolecules,2017,50:5695.
[27] Nakahata M,Takashima Y,Yamaguchi H,Harada A. Nat.Commun.,2011,2:511.
[28] Zhang Y N,Yang D,Han J L,Zhou J,Jin Q X,Liu M H,Duan P F. Langmuir,2018,34:5821.
[29] Li Y Y,Liu J,Du G Y,Yan H,Wang H Y,Zhang H C,An W,Zhao W J,Sun T,Xin F F,Kong L,Li Y M,Hao A Y,Hao J C. J. Phys. Chem. B,2010,114:10321.
[30] Li Y Y,Zhao W J,Zhang H C,Sun T,An W,Xin F F,Hao A Y. Chinese Chem. Lett.,2010,21:1251.
[31] Zhao W J,Li Y Y,Sun T,Yan H,Hao A Y,Xin F F,Zhang H C,An W,Kong L,Li Y M. Colloids Surf. A,2011,374:115.
[32] Xin F F,Zhang H C,Hao B X,Sun T,Kong L,Li Y M,Hou Y H,Li S Y,Zhang Y,Hao A Y. Colloids Surf. A,2012,410:18.
[33] Xing P Y,Chu X X,Li S Y,Xin F F,Ma M F,Hao A Y. New J. Chem.,2013,37:3949.
[34] Li Z L,Liu W Q,Hao A Y. Colloids Surf. A,2014,451:25.
[35] Li Z L,Hao A Y,Li X. J. Mol. Liq.,2014,196:52.
[36] Kong L,Xing P Y,Chu X X,Hao A Y. J. Control. Release2017,259:e77.
[37] Hou Y H,Xin F F,Yin M J,Kong L,Zhang H C,Sun T,Xing P Y,Hao A Y. Colloids Surf. A,2012,414:160.
[38] Xing P Y,Chu X X,Li S Y,Hou Y H,Ma M F,Yang J S,Hao A Y. RSC Adv.,2013,3:22087.
[39] Hou Y H,Li S Y,Sun T,Yang J S,Xing P Y,Liu W Q,Hao A Y. J. Incl. Phenom. Macrocycl. Chem. 2014,80:217.
[40] Kong L,Sun T,Xin F F,Zhao W J,Zhang H C,Li Z L,Li Y M,Hou Y H,Li S Y,Hao A Y. Colloids Surf. A,2011,392:156.
[41] Liu W Q,Xing P Y,Xin F F,Hou Y H,Sun T,Hao J C,Hao A Y. J. Phys. Chem. B,2012,116:13106.
[42] Ma X,Tian H. Acc. Chem. Res.,2014,47:1971.
[43] Qu D H,Wang Q C,Ren J,Tian H. Org. Lett.,2004,6:2085.
[44] Li Y G,Liu M. H. J. Colloid Interf. Sci.,2007,306:386.
[45] Ma X,Cao J J,Wang Q C,Tian H. Chem. Commun.,2011,47:3559.
[46] Xing P Y,Sun T,Li S Y,Hao A Y,Su J,Hou Y H. Colloids Surf. A,2013,421:44.
[47] Hou Y H,Sun T,Xin F F,Xing P Y,Li S Y,Hao A Y. J.Incl. Phenom. Macrocycl. Chem.,2014,79:133.
[48] Chu X X,Xing P Y,Li S Y,Ma M F,Hao A Y. Colloids Surf.A,2014,461:11.
[49] Saenger W,Jacob J,Gessler K,Steiner T,Hoffmann D,Sanbe H,Koizumi K,Smith S M,Takaha T. Chem. Rev.,1998,5:1787.
[50] Xin F F,Xing P Y,Li S Y,Hou Y H,Hao A Y. RSC Adv.,2013,3:21959.
[51] Chen Y,Zhang Y M,Liu Y. Chem. Commun.,2010,46:5622.
[52] Gao Y A,Zhao X Y,Dong B,Zheng L Q,Li N,Zhang S H. J.Phys. Chem. B,2006,110:8576.
[53] Li Z L,Hao A Y,Hao J C. Colloids Surf. A,2014,441:8.
[54] Xing P Y,Li S Y,Xin F F,Hou Y H,Hao A Y,Sun T,Su J.Carbohydra. Res.,2016,367:18.
[55] Li Z L,Zhang B,Jia S H,Ma M F,Hao J C. J. Mol. Liq.,2018,250:19.
[56] Kong L,Zhang F,Xing P Y,Chu X X,Hao A Y. Colloids Surf.A,2017,522:577.
[2] Hisamatsu Y, Banerjee S, Avinash M B, Govindaraju T,Schmuck T. Angew. Chem. Int. Ed.,2013,52:12550.
[3] Tam A Y,Wong K M,Yam V W. Chem. Eur. J.,2009,15:4775.
[4] Ma M F,Gu J G,Yang M M,Li Z L,Lu Z Q,Zhang Y M,Xing P Y,Li S Y,Chu X X,Wang Y J,Li Q,Lin M Y,Hao A Y. RSC Adv.,2015,5:70178.
[5] Xing P Y, Chu X X, Li S Y, Ma M F, Hao A Y.ChemPhysChem,2014,15:2377.
[6] Xing P Y,Chu X X,Ma M F,Li S Y,Hao A Y. Chem. Asian J.,2014,9:3440.
[7] Sui J F,Wang L H,Zhao W R,Hao J C. Chem. Commun.,2016,52:6993.
[8] Song S S,Feng L,Song A X,Hao J C. J. Phys. Chem. B,2012,116:12850.
[9] Nanda J,Biswas A,Adhikari B,Banerjee A. Angew. Chem. Int.Ed.,2013,52:5041.
[10]童林荟(Tong L H).环糊精化学———基础与应用(Cyclodextrin Chemistry———Foundation and Application).北京:科学出版社(Beijing:Science Press),2001. 10.
[11] Sun T,Li Y M,Zhang H C,Li J Y,Xin F F,Kong L,Hao A Y. Colloids Surf. A,2011,375:87.
[12] Sun T,Guo Q,Zhang C,Hao J C,Xing P Y,Li S Y,Hao A Y,Liu G C. Langmuir,2012,28:8625.
[13] Sun T,Zhang H C,Kong L,Qiao H W,Li Y M,Xin F F,Hao A Y. Carbohydra. Res.,2011,346:285.
[14] Ma M F,Su J,Sheng X,Su F,Li S Y,Xing P Y,Hao A Y. J.Mol. Liq.,2014,198:1.
[15] Zhou C C,Cheng X H,Zhao Q,Yan Y,Wang J D,Huang J B.Scientific Reports,2014,4:7355.
[16] Zhou C C,Huang J B,Yan Y. Soft Matter,2016,12:1579.
[17] Chen L,Chen H,Yao X Y,Ma X,Tian H. Chem-Asian J.,2015,10:2352.
[18] Chen H,Ma X,Wu S F,Tian H. Angew. Chem.,2014,126:14373.
[19] Zhang Q W,Qu D H,Wu J C,Ma X,Wang Q C,Tian H.Langmuir,2013,29:5345.
[20] Nakahata M,Takashima Y,Harada A. Angew. Chem. Int. Ed.,2014,53:3617.
[21] Miyamae K,Nakahata M,Takashima Y,Harada A. Angew.Chem. Int. Ed.,2015,54:8984.
[22] Kakuta T,Takashima Y,Sano T,Nakamura T,Kobayashi Y,Yamaguchi H,Harada A. Macromolecules,2015,48:732.
[23] Nakahata M,Takashima Y,Harada A. Macromol. Rapid Comm.,2015,37:86.
[24] Zheng Y T,Kobayashi Y,Sekine T,Takashima Y,Hashidzume A,Yamaguchi H, Harada A. Nat. Commun., 2018, DOI:10. 1038/s42004-017-0003-x.
[25] Takashima Y,Sawa Y,Iwaso K,Nakahata M,Yamaguchi H,Harada A. Macromolecules,2017,50:3254.
[26] Koyanagi K, Takashima Y, Yamaguchi H, Harada A.Macromolecules,2017,50:5695.
[27] Nakahata M,Takashima Y,Yamaguchi H,Harada A. Nat.Commun.,2011,2:511.
[28] Zhang Y N,Yang D,Han J L,Zhou J,Jin Q X,Liu M H,Duan P F. Langmuir,2018,34:5821.
[29] Li Y Y,Liu J,Du G Y,Yan H,Wang H Y,Zhang H C,An W,Zhao W J,Sun T,Xin F F,Kong L,Li Y M,Hao A Y,Hao J C. J. Phys. Chem. B,2010,114:10321.
[30] Li Y Y,Zhao W J,Zhang H C,Sun T,An W,Xin F F,Hao A Y. Chinese Chem. Lett.,2010,21:1251.
[31] Zhao W J,Li Y Y,Sun T,Yan H,Hao A Y,Xin F F,Zhang H C,An W,Kong L,Li Y M. Colloids Surf. A,2011,374:115.
[32] Xin F F,Zhang H C,Hao B X,Sun T,Kong L,Li Y M,Hou Y H,Li S Y,Zhang Y,Hao A Y. Colloids Surf. A,2012,410:18.
[33] Xing P Y,Chu X X,Li S Y,Xin F F,Ma M F,Hao A Y. New J. Chem.,2013,37:3949.
[34] Li Z L,Liu W Q,Hao A Y. Colloids Surf. A,2014,451:25.
[35] Li Z L,Hao A Y,Li X. J. Mol. Liq.,2014,196:52.
[36] Kong L,Xing P Y,Chu X X,Hao A Y. J. Control. Release2017,259:e77.
[37] Hou Y H,Xin F F,Yin M J,Kong L,Zhang H C,Sun T,Xing P Y,Hao A Y. Colloids Surf. A,2012,414:160.
[38] Xing P Y,Chu X X,Li S Y,Hou Y H,Ma M F,Yang J S,Hao A Y. RSC Adv.,2013,3:22087.
[39] Hou Y H,Li S Y,Sun T,Yang J S,Xing P Y,Liu W Q,Hao A Y. J. Incl. Phenom. Macrocycl. Chem. 2014,80:217.
[40] Kong L,Sun T,Xin F F,Zhao W J,Zhang H C,Li Z L,Li Y M,Hou Y H,Li S Y,Hao A Y. Colloids Surf. A,2011,392:156.
[41] Liu W Q,Xing P Y,Xin F F,Hou Y H,Sun T,Hao J C,Hao A Y. J. Phys. Chem. B,2012,116:13106.
[42] Ma X,Tian H. Acc. Chem. Res.,2014,47:1971.
[43] Qu D H,Wang Q C,Ren J,Tian H. Org. Lett.,2004,6:2085.
[44] Li Y G,Liu M. H. J. Colloid Interf. Sci.,2007,306:386.
[45] Ma X,Cao J J,Wang Q C,Tian H. Chem. Commun.,2011,47:3559.
[46] Xing P Y,Sun T,Li S Y,Hao A Y,Su J,Hou Y H. Colloids Surf. A,2013,421:44.
[47] Hou Y H,Sun T,Xin F F,Xing P Y,Li S Y,Hao A Y. J.Incl. Phenom. Macrocycl. Chem.,2014,79:133.
[48] Chu X X,Xing P Y,Li S Y,Ma M F,Hao A Y. Colloids Surf.A,2014,461:11.
[49] Saenger W,Jacob J,Gessler K,Steiner T,Hoffmann D,Sanbe H,Koizumi K,Smith S M,Takaha T. Chem. Rev.,1998,5:1787.
[50] Xin F F,Xing P Y,Li S Y,Hou Y H,Hao A Y. RSC Adv.,2013,3:21959.
[51] Chen Y,Zhang Y M,Liu Y. Chem. Commun.,2010,46:5622.
[52] Gao Y A,Zhao X Y,Dong B,Zheng L Q,Li N,Zhang S H. J.Phys. Chem. B,2006,110:8576.
[53] Li Z L,Hao A Y,Hao J C. Colloids Surf. A,2014,441:8.
[54] Xing P Y,Li S Y,Xin F F,Hou Y H,Hao A Y,Sun T,Su J.Carbohydra. Res.,2016,367:18.
[55] Li Z L,Zhang B,Jia S H,Ma M F,Hao J C. J. Mol. Liq.,2018,250:19.
[56] Kong L,Zhang F,Xing P Y,Chu X X,Hao A Y. Colloids Surf.A,2017,522:577.