基于修饰的β-环糊精的超分子体系研究及应用进展

doi:10.11944/j.issn.1000-0518.2017.02.160282

摘要/Abstract

摘要：

β-环糊精是一类环状的、由7个D-吡喃葡萄糖单元通过α-1,4-糖苷键连接而成的低聚糖,具有“内疏水、外亲水”的刚性锥形空腔结构。近年来,基于β-环糊精的超分子体系的制备及应用取得前所未有的显著进展。本文主要综述了β-环糊精衍生物、低聚物以及多聚物在合成方面的新进展,介绍了基于β-环糊精的分子组装,以及以β-环糊精及其修饰物为超分子主体的超分子体系在药物运输、基因传递、催化反应、污染治理等方面的最新应用。目前,对β-环糊精基本性质及应用的研究已日趋成熟,但仍存在许多实际性的问题需要解决。随着研究的进一步深入,有望实现β-环糊精在各领域的大规模、深层次应用。

关键词: β-环糊精, 修饰物, 超分子, 组装, 应用

Abstract:

β-Cyclodextrin(β-CD) is a class of cyclic oligosaccharide which consists of seven D-galactose units linked by α-1,4-glycosidic bonds. β-CD has a rigid and cone-like molecular structure with hydrophilic outer surface and hydrophobic inner cavity. Recently, unprecedented progress about the preparation and application of supramolecular system based on β-CD has been made. In this paper, the synthesis of derivatives, oligomers and polymers of β-CD, molecular assemblies based on β-CD, and their latest application of supramolecular system that uses β-CD and its modifier as host in drug delivery, gene transfer, catalytic reaction, pollution control and so on, are reviewed. Until now, studies on basic properties of β-CD are becoming mature, but there are still some realistic problems remaining to be solved. With further studies, wider and deeper applications of β-CD may be finally achieved in various fields.

Key words: β-cyclodextrin, modifier, supramolecular, assembly, application

李琳琳,段尊斌,朱丽君,项玉芝,夏道宏. 基于修饰的β-环糊精的超分子体系研究及应用进展[J]. 应用化学, 2017, 34(2): 123-138.

LI Linlin,DUAN Zunbin,ZHU Lijun,XIANG Yuzhi,XIA Daohong. Progress in Study and Application of Supramolecular System Based on β-Cyclodextrin[J]. Chinese Journal of Applied Chemistry, 2017, 34(2): 123-138.

参考文献

[1]	Steed J W,Atwood J L. Supramolecular Chemistry[M]. ZHAO Yaopeng,SUN Zhen,Trans. Beijing: Chemical Industry Press,2006:1-2(in Chinese). 斯蒂德 J W,阿特伍德 J L. 超分子化学[M]. 赵耀鹏,孙震译,译.北京: 化学工业出版社,2006:1-2.
[2]	Lehn J M. Supramolecular Chemistry:Concepts and Perspectives[M]. Weinheim:VCH,1995.
[3]	Wang Z Z,Fu X Y,Dai G D,et al.Efficient and Improved Syntheses of Two Key Intermediates for Functionalization of β-Cyclodextrin at the Secondary Hydroxyl Face[J]. Monatsh Chem,2011,142(3):317-319.
[4]	Yu J,Zuo L H,Liu H J,et al.Synthesis and Application of a Chiral Ionic Liquid Functionalized β-Cyclodextrin as a Chiral Selector in Capillary Electrophoresis[J]. Biomed Chromatogr,2013,27(8):1027-1033.
[5]	Zhang L F,Zhang Z H,Li N,et al.Synthesis and Evaluation of a Novel β-Cyclodextrin Derivative for Oral Insulin Delivery and Absorption[J]. Int J Biol Macromol,2013,61:494-500.
[6]	García A,Leonardi D,Lamas M C. Promising Applications in Drug Delivery Systems of a Novel β-Cyclodextrin Derivative Obtained by Green Synthesis[J]. Bioorg Med Chem Lett,2016,26(2):602-608.
[7]	Chen Y,Liu Y. Cyclodextrin-based Bioactive Supramolecular Assemblies[J]. Chem Soc Rev,2010,39(2):495-505.
[8]	Tang B,Liang H L,Xu K H,et al.An Improved Synthesis of Disulfides Linked β-Cyclodextrin Dimer and Its Analytical Application for Dequalinium Chloride Determination by Spectrofluorimetry[J]. Anal Chim Acta,2005,554(1/2): 31-36.
[9]	Chen D M,Chen Z Z,Xu K H,et al.Studies on the Supramolecular Interaction Between Dimethomorph and Disulfide Linked β-Cyclodextrin Dimer by Spectrofluorimetry and Its Analytical Application[J]. J Agric Food Chem,2011,59(9):4424-4428.
[10]	Casas-Solvas J M,Martos-Maldonado M C,Vargas-berenguel A. Synthesis of β-Cyclodextrin Derivatives Functionalized with Azobenzene[J]. Tetrahedron,2008,64(48):10919-10923.
[11]	Ma H C,Wang F,Li W F,et al.Supramolecular Assemblies of Azobenzene-β-Cyclodextrin Dimers and Azobenzene Modified Polycaprolactones[J]. J Phys Org Chem,2014,27(9):722-728.
[12]	Kuad P,Miyawaki A,Takashima Y,et al.External Stimulus-responsive Supramolecular Structures Formed by a Stilbene Cyclodextrin Dimer[J]. J Am Chem Soc,2007,129(42):12630-12631.
[13]	Morin-Crini N,Crini G. Environmental Applications of Water-insoluble-cyclodextrin-epichlorohydrin Polymers[J]. Prog Polym Sci,2013,38(2):344-368.
[14]	Alsbaiee A,Smith B J,Xiao L L,et al.Rapid Removal of Organic Micropollutants from Water by a Porous β-Cyclodextrin Polymer[J]. Nature,2016,529(7585):190-U146.
[15]	Yang S Y,Hoonor R,Jin H S,et al.Synthesis and Characterization of Cationic and Anionic Cyclodextrin Oligomers and Their Use in Layer-by-Layer Film Formation[J]. Bull Korean Chem Soc,2013,34(7):2016-2022.
[16]	LIAO Ping,HE Ping,WANG Yu,et al.Process on Nano-assembly Based on Cyclodextrins[J]. Chem World,2009,50(3):178-185(in Chinese). 廖萍,何平,王玉,等. 基于环糊精的纳米功能组装体的研究进展[J]. 化学世界,2009,50(3):178-185.
[17]	Liu Y,Yu L,Chen Y,et al.Construction and DNA Condensation of Cyclodextrin-based Polypseudorotaxanes with Anthryl Grafts[J]. J Am Chem Soc,2007,129(35):10656-10657.
[18]	Gonzalez H,Hwang S J,Davis M E. New Class of Polymers for the Delivery of Macromolecular Therapeutics[J]. J Am Chem Soc,1999,10(6):1068-1074.
[19]	Davis M E,Brewster M E. Cyclodextrin-based Pharmaceutics:Past, Present and Future[J]. Nat Rev Drug Discovery,2004,3(12):1023-1035.
[20]	Li J,Yang C,Li H Z,et al.Cationic Supramoleculars Composed of Multiple Oligoethylenimine-grafted β-Cyclodextrins Threaded on a Polymer Chain for Efficient Gene Delivery[J]. Adv Mater,2006,18(22):2969-2974.
[21]	Li J,Loh X. Cyclodextrin-based Supramolecular Architectures: Syntheses, Structures, and Applications for Drug and Gene Delivery[J]. Adv Drug Delivery Rev,2008,60(9):1000-1017.
[22]	Mathew A,Natarajan G,Lehtowaara L,et al.Supramolecular Functionalization and Concomitant Enhancement in Properties of Au25 Clusters[J]. J Am Chem Soc,2014,8(1):139-152.
[23]	Chen Y,Liu Y. Construction and Functions of Cyclodextrin-based 1D Supramolecular Strands and Their Secondary Assemblies[J]. Adv Mater,2015,27(36):5403-5409.
[24]	Liu Y,Yang Y W,Chen Y,et al.Polyrotaxane with Cyclodextrins as Stoppers and Its Assembly Behavior[J]. Macromolecules,2005,38(13):5838-5840.
[25]	Ke C F,Hou S,Zhang H Y,et al.Controllable DNA Condensation Through Cucurbit[6]uril in 2D Pseudopolyrotaxanes[J]. Chem Commun,2007,32(32):3374-3376.
[26]	Li Z Q,Zhang Y M,Chen Y,et al.A Supramolecular Tubular Nanoreactor[J]. Chem Eur J,2014,20(28):8566-8570.
[27]	Sun H L,Chen Y,Zhao J,et al.Photocontrolled Reversible Conversion of Nanotube and Nanoparticle Mediated by β-Cyclodextrin Dimers[J]. Angew Chem Int Ed,2015,54(32):9376-9380.
[28]	Guo M Y,Jiang M,Pispas S,et al.Supramolecular Hydrogels Made of End-functionalized Low-molecular-weight PEG and R-cyclodextrin and Their Hybridization with SiO2 Nanoparticles Through Host-guest Interaction[J]. Macromolecules,2008,41(24):9744-9749.
[29]	Liu J H,Chen G S,Guo M,et al.Dual Stimuli-Responsive Supramolecular Hydrogel Based on Hybrid Inclusion Complex(HIC)[J]. Macromolecules,2010,43(19):8086-8093.
[30]	Liu J H,Chen G S,Jiang M. Supramolecular Hybrid Hydrogels from Noncovalently Functionalized Graphene with Block Copolymers[J]. Macromolecules,2011,44(19):7682-7691.
[31]	Du P,Liu J H,Chen G S,et al.Dual Responsive Supramolecular Hydrogel with Electrochemical Activity[J]. Langmuir,2011,27(15):9602-9608.
[32]	Du P,Chen G S,Jiang M. Electrochemically Sensitive Supra-crosslink and Its Corresponding Hydrogel[J]. Sci China Chem,2012,55(5):836-843.
[33]	Tao W,Liu Y,Jiang B B,et al.A Linear-hyperbranched Supramolecular Amphiphile and Its Self Assembly into Vesicles with Great Ductility[J]. J Am Chem Soc,2012,134(2):762-764.
[34]	Liu Y,Yu C Y,Jin H B,et al.A Supramolecular Janus Hyperbranched Polymer and Its Photoresponsive Self-assembly of Vesicles with Narrow Size Distribution[J]. J Am Chem Soc,2013,135(12):4765-4770.
[35]	LI Huimei,WANG Jie,NI Yunzhou,et al.Synthesis of a Linear-hyperbranched Supramolecular Polymer and Its Light-responsive Self-assembly Behavior[J]. Acta Chim Sin,2016,74(5):415-421(in Chinese). 李惠梅,王洁,倪云洲,等. “线性-超支化”超分子聚合物的制备及光响应性自组装行为研究[J]. 化学学报,2016,74(5):415-421.
[36]	Dong R J,Chen H Y,Wang D L,et al.Supramolecular Fluorescent Nanoparticles for Targeted Cancer Imaging[J]. ACS Macro Lett,2012,1(10):1208-1211.
[37]	Li Q L,Wang L Z,Qiu X L,et al.Stimuli-responsive Biocompatible Nanovalves Based on β-Cyclodextrin Modified Poly(glycidyl methacrylate)[J]. Polym Chem,2014,5(10):3389-3395.
[38]	Gu W X,Li Q L,Lu H G,et al.Construction of Stable Polymeric Vesicles Based on Azobenzene and Beta-cyclodextrin Grafted Poly(glycerol methacrylate)s for Potential Applications in Colon-specific Drug Delivery[J]. Chem Commun,2015,51(22):4715-4718.
[39]	Toomari Y,Namazi H,Akbar E A. Synthesis of the Dendritic Type β-Cyclodextrin on Primary Face via Click Reaction Applicable as Drug Nanocarrier[J]. Carbohydr Polym,2015,132:205-213.
[40]	Yin J J,Sharma S,Shumyak S P,et al.Synthesis and Biological Evaluation of Novel Folic Acid Receptor-targeted, β-Cyclodextrin-based Drug Complexes for Cancer Treatment[J]. Plos One,2013,8(5):e62289.
[41]	Tofzikovskaya Z,Casey A,Howe O,et al.In Vitro Evaluation of the Cytotoxicity of a Folate-modified β-Cyclodextrin as a New Anti-cancer Drug Delivery System[J]. J Inclus Phenom Macrocyclic Chem,2015,81(1/2):85-94.
[42]	Shu C,Li R X,Guo J,et al.New Generation of β-Cyclodextrin-chitosan Nanoparticles Encapsulated Quantum Dots Loaded with Anticancer Drug for Tumor-target Drug Delivery and Imaging of Cancer Cells[J]. J Nanopart Res,2013,15(12):1-14.
[43]	Shi Y J,Chang S,Cui W Y,et al.Gefitinib Loaded Folate Decorated Bovine Serum Albumin Conjugated Carboxymethyl-beta-cyclodextrin Nanoparticles Enhance Drug Delivery and Attenuate Autophagy in Folate Receptor-positive Cancer Cells[J]. J Nanobiotechnol,2014,12(1):1-11.
[44]	Huang X,Yi C X,Fan Y J,et al.Magnetic Fe3O4 Nanoparticles Grafted with Single-chain Antibody(scFv) and Docetaxel Loaded β-Cyclodextrin Potential for Ovarian Cancer Dual-targeting Therapy[J]. Mater Sci Eng C,2014,42:325-332.
[45]	Wei G C,Dong R H,Wang D,et al.Functional Materials from the Covalent Modification of Reduced Graphene Oxide and β-Cyclodextrin as a Drug Delivery Carrier[J]. New J Chem,2014,38(1):140-145.
[46]	Ye Y J,Sun Y,Zhao H L,et al.A Novel Lactoferrin-modified β-Cyclodextrin Nanocarrier for Brain-targeting Drug Delivery[J]. Int J Pharm,2013,458(1):110-117.
[47]	Li R C,Zhang X T,Zhang Q Y,et al.β-Cyclodextrin-conjugated Hyaluronan Hydrogel as a Potential Drug Sustained Delivery Carrier for Wound Healing[J]. J Appl Polym Sci,2016,133(9):1-8.
[48]	Ping Y,Hu Q D,Tang G P,et al.FGFR-targeted Gene Delivery Mediated by Supramolecular Assembly Between β-Cyclodextrin-crosslinked PEI and Redox-sensitive PEG[J]. Biomaterials,2013,34(27):6482-6494.
[49]	Li R Q,Niu Y L,Zhao N N,et al.Series of New β-Cyclodextrin-cored Starlike Carriers for Gene Delivery[J]. ACS Appl Mater Interfaces,2014,6(6):3969-3978.
[50]	Yin H,Zhao F,Zhang D H,et al.Hyaluronic Acid Conjugated β-Cyclodextrin-oligoethylenimine Star Polymer for CD44-targeted Gene Delivery[J]. Int J Pharm,2015,483(1-2):169-179.
[51]	Liang L Y,Diallo A K.,Salmon L,et al.Catalysis of C—C Cross-coupling Reactions in Aqueous Solvent by Bis- and Tris(ferrocenyltriazolylmethyl)arene-β-cyclodextrin-Stabilized, Pd0 Nanoparticles[J]. Eur J Inorg Chem,2012,17:2950-2958.
[52]	Decottignies A,Fihri A,Azemar G,et al.Ligandless Suzuki-Miyaura Reaction in Neat Water with or Without Native β-Cyclodextrin as Additive[J]. Catal Commun,2013,32:101-107.
[53]	Potier J,Menuel S,Monflier E,et al.Synergetic Effect of Randomly Methylated β-Cyclodextrin and a Supramolecular Hydrogel in Rh-catalyzed Hydroformylation of Higher Olefins[J]. J Am Chem Soc,2014,4(7):2342-2346.
[54]	He K C,Qiu F X,Qin J,et al.Preparation and Characterization of L-Phenylalanine-derivatized β-Cyclodextrin-bonded Silica and Its Application on Chiral Separation of Alanine Acid Racemates[J]. Korean J Chem Eng,2013,30(11):2078-2087.
[55]	Hong J S,Park J H. Chiral Separation of Basic Compounds on Sulfated β-Cyclodextrin-coated Zirconia Monolith by Capillary Electrochromatography[J]. Bull Korean Chem Soc,2013,34(6):1809-1813.
[56]	Chang Y X,Bai B,Du L M,et al.Effect of Single-walled Carbon Nanotubes on Hydroxypropyl-β-cyclodextrin Stationary Phase[J]. J Chil Chem Soc,2013,58(58):2209-2212.
[57]	Bhattarai B,Muruganandham M, Suri R P S. Development of High Efficiency Silica Coated β-Cyclodextrin Polymeric Adsorbent for the Removal of Emerging Contaminants of Concern from Water[J]. J Hazard Mater,2014,273:146-154.
[58]	Mamba G,Mbianda X Y,Govender P P. Phosphorylated Multiwalled Carbon Nanotube-Cyclodextrin Polymer:Synthesis, Characterisation and Potential Application in Water Purification[J]. Carbohydr Polym,2013,98(1):470-476.
[59]	Kyzas G Z,Lazaridis N K,Bikiaris D N. Optimization of Chitosan and β-Cyclodextrin Molecularly Imprinted Polymer Synthesis for Dye Adsorption[J]. Carbohydr Polym,2013,91(1):198-208.
[60]	Mangolim C S,Moriwaki C,Nogueira A C,et al.Curcumin-β-Cyclodextrin Inclusion Complex:Stability, Solubility, Characterisation by FT-IR, FT-Raman, X-ray Diffraction and Photoacoustic Spectroscopy, and Food Application[J]. Food Chem,2014,153(153):361-370.
[61]	Jeong Y K,Kwon T,Lee I,et al.Multidimensional Binder for Silicon Anodes in Lithium Rechargeable Batteries[J]. Nano Lett,2014,14(2):864-870.
[62]	Liu X J,Jiang W C,Gou S H. Synthesis and Evaluation of Novel Water-soluble Copolymers Based on Acrylamide and Modular β-Cyclodextrin[J]. Carbohydr Polym,2013,96(1):47-56.
[63]	Sun Y,Xia D H,Xiang Y Z. A Novel Method for Removing Sulfur Compounds from Light Oil by Molecular Recognition with β-Cyclodextrin[J]. Pet Sci Technol,2008,26(17):2023-2032.
[64]	XIA Daohong,DUAN Zunbin,BU Tingting,et al. A Light Oil Desulfrizer and Its Usage Based on Supramolecular Inclusion:CN,2015105126768.A[P].2015-12-09(in Chinese). 夏道宏,段尊斌,卜婷婷,等. 一种基于超分子包合作用的轻质油品脱硫剂及其使用方法:中国,2015105126768.A[P].2015-12-09.
[65]	XIA Daohong,BU Tingting,DUAN Zunbin,et al. A Fuel Oil Denitrifier and Its Usage Based on Supramolecular Inclusion:CN,2015105087050.A[P].2015-11-25(in Chinese). 夏道宏,卜婷婷,段尊斌,等. 一种利用超分子包合作用的燃料油品脱氮剂及其使用方法:中国,2015105087050.A[P].2015-11-25.
[66]	Duan Z B,Li L L,Bu T T,et al. A Green & Natural Method for Removing of Nitride from Light Oil by β-Cyclodextrin Aqueous Solution Through Molecular Recognition[C]//The Second Annual International Conference on Energy, Environmental & Sustainable Ecosystem Development. Kunming,2016:N/A.