Citation: Jing Dang, Yuan-Wei Su, Wei Tian. Cyclodextrin-functionalized Ordered Porous Block Copolymer Films: Preparation and Property[J]. Chinese Journal of Polymer Science, ;2018, 36(1): 34-42. doi: 10.1007/s10118-018-2005-2 shu

Cyclodextrin-functionalized Ordered Porous Block Copolymer Films: Preparation and Property

Jing Dang ^† ,
Yuan-Wei Su ^† ,
Wei Tian ^,

Ministry of Education Key Laboratory of Material Physics and Chemistry under Extraordinary Conditions and Shaanxi Key Laboratory of Macromolecular Science and Technology, School of Science, Northwestern Polytechnical University, Xi'an 710072, China

Corresponding author: Wei Tian, happytw_3000@nwpu.edu.cn

^†

Received Date: 9 May 2017
Revised Date: 3 July 2017
Accepted Date: 3 July 2017
Available Online: 22 September 2017

Ordered porous block copolymer films (PBCFs) have attracted much attention because of their potential applications in several fields. In this paper, we first reported a non-destructive, controllable, and efficient approach for preparation of β-cyclodextrin (β-CD)-functionalized PBCFs (β-CD-PBCFs). The key point of the approach is to incorporate β-CD units into the hydrophilic segment of amphiphilic block copolymers before the preparation of films. β-CD-PBCFs with structural integrity and controllable pore parameters were fabricated through combining of self-assembly and breath figure methods. And then, the effective adsorption capacity of β-CD-PBCFs toward Congo red was confirmed through UV-Vis spectroscopy and was found to be affected by β-CD content and solution pH values. Adsorption kinetic results showed that the adsorption behavior of β-CD-PBCFs was consistent with the pseudo-second-order kinetic model and the chemisorption mechanism.
- Porous block copolymer film,
- β-Cyclodextrin,
- Breath figure,
- Self-assembly
1. [1]
  Corma A., Davis M. E.. Issues in the synthesis of crystalline molecular sieves:towards the crystallization of low framework-density structures[J]. ChemPhysChem., 2004,5(3):304-313. doi: 10.1002/(ISSN)1439-7641
2. [2]
  Davis M. E.. Ordered porous materials for emerging applications[J]. Nature, 2002,417(6891):813-821. doi: 10.1038/nature00785
3. [3]
  Toniolo R., Comisso N., Schiavon G., Bontempelli G.. Porous electrodes supported on ion-exchange membranes as electrochemical detectors for supercritical fluid chromatography[J]. Anal. Chem., 2004,76(7):2133-2137. doi: 10.1021/ac0351421
4. [4]
  Galeazzo E., Peres H. E. M., Santos G., Peixoto N.. Gas sensitive porous silicon devices:responses to organic vapors[J]. Sensor. Actuator. B-Chem., 2003,93(1):384-390.
5. [5]
  Jackson E. A., Hillmeyer M. A.. Nanoporous membranes derived from block copolymers:from drug delivery to water filtration[J]. ACS Nano, 2010,4(7):3548-3553. doi: 10.1021/nn1014006
6. [6]
  de Boer B., Stalmach U., Nijland H., Hadziioannou G.. Microporous honeycomb-structured films of semiconducting block copolymers and their use as patterned templates[J]. Adv. Mater., 2000,12(21):1581-1583. doi: 10.1002/(ISSN)1521-4095
7. [7]
  Yang S., Yang J. A., Kim E. S.. Single-file diffusion of protein drugs through cylindrical nanochannels[J]. ACS Nano, 2010,4(7):3817-3822. doi: 10.1021/nn100464u
8. [8]
  Cai T., Li M., Zhang B., Neoh K. G., Kang E. T.. Hyperbranched polycaprolactone-click-poly(N-vinylcaprolactam) amphiphilic copolymers and their applications as temperature-responsive membranes[J]. J. Mater. Chem. B, 2014,2(7):814-825. doi: 10.1039/C3TB20752H
9. [9]
  Cai T., Li M., Neoh K. G., Kang E. T.. Surface-functionalizable membranes of polycaprolactone-click-hyperbranched polyglycerol copolymers from combined atom transfer radical polymerization, ring-opening polymerization and click chemistry[J]. J. Mater. Chem. B, 2013,1(9):1304-1315. doi: 10.1039/c2tb00273f
10. [10]
  Cai T., Wang R., Yang W. J., Neoh K. G., Kang E. T.. Multi-functionalization of poly (vinylidene fluoride) membranes via combined "grafting from" and "grafting to" approaches[J]. Soft Matter, 2011,7(23):11133-11143. doi: 10.1039/c1sm06039b
11. [11]
  Hillmyer M. A.. Nanoporous materials from block copolymer precursors[J]. Adv. Polym. Sci., 2005,190:137-181. doi: 10.1007/b138192
12. [12]
  Olson D. A., Chen L., Hillmyer M. A.. Templating nanoporous polymers with ordered block copolymers[J]. Chem. Mater., 2007,20(3):869-890.
13. [13]
  Hamley I. W.. Nanostructure fabrication using block copolymers[J]. Nanotechnology, 2003,14(10):39-54. doi: 10.1088/0957-4484/14/10/201
14. [14]
  Lee J. S., Hirao A., Nakahama S.. Polymerization of monomers containing functional silyl groups. 5. Synthesis of new porous membranes with functional groups[J]. Macromolecules, 1988,21(1):274-276.
15. [15]
  Jackson E. A., Hillmye M. A.. Nanoporous membranes derived from block copolymers:from drug delivery to water filtration[J]. ACS Nano, 2010,4(7):3548-3553. doi: 10.1021/nn1014006
16. [16]
  Yave W., Car A., Funari S. S., Nunes S. P., Peinemann K. V.. CO₂-philic polymer membrane with extremely high separation performance[J]. Macromolecules, 2009,43(1):326-333.
17. [17]
  Thurn-Albrecht T., Schotter J., Kastle C. A., Emley N., Shibauchi T., Krusin-Elbaum L., Guarini K., Black C. T., Tuominen M. T., Russell T. P.. Ultrahigh-density nanowire arrays grown in self-assembled diblock copolymer templates[J]. Science, 2000,290(5499):2126-2129. doi: 10.1126/science.290.5499.2126
18. [18]
  Liang J., Ma Y. Y., Sims S., Wu L. X.. A patterned porous polymer film for localized capture of insulin and glucose-responsive release[J]. J. Mater. Chem. B, 2015,3(7):1281-1288. doi: 10.1039/C4TB01537A
19. [19]
  Clodt J. I., Abetz V.. Double stimuli-responsive isoporous membranes via post-modification of pH-sensitive self-assembled diblock copolymer membranes[J]. Adv. Funct. Mater., 2013,23(6):731-738. doi: 10.1002/adfm.v23.6
20. [20]
  Connal L. A., Vestberg R., Hawker C. J., Qiao G. G.. Dramatic morphology control in the fabrication of porous polymer films[J]. Adv. Funct. Mater., 2008,18(22):3706-3714. doi: 10.1002/adfm.v18:22
21. [21]
  Schacher F., Ulbricht M., Muller A. H. E.. Self-supporting, double stimuli-responsive porous membranes from polystyrene-block-poly(N, N-dimethylaminoethyl methacrylate) diblock copolymers[J]. Adv. Funct. Mater., 2009,19(7):1040-1045.
22. [22]
  Li Y., Ito T.. Surface chemical functionalization of cylindrical nanopores derived from a polystyrene-poly(methylmethacrylate) diblock copolymer via amidation[J]. Langmuir, 2008,24(16):8959-8963. doi: 10.1021/la800992f
23. [23]
  Yamaguchi T., Ito T., Sato T., Shinbo T., Nakao S.. Development of a fast response molecular recognition ion gating membrane[J]. J. Am. Chem. Soc., 1999,121(16):4078-4079. doi: 10.1021/ja984170b
24. [24]
  Yang J. M., Yang J. H., Huang H. T.. Chitosan/polyanion surface modification of styrene-butadiene-styrene block copolymer membrane for wound dressing[J]. Mater. Sci. Eng. C, 2014,34:140-148. doi: 10.1016/j.msec.2013.09.001
25. [25]
  Widawski G., Rawiso M., Francois B.. Self-organized honeycomb morphology of star-polymer polystyrene films[J]. Nature, 1994,369(6479):387-389. doi: 10.1038/369387a0
26. [26]
  Wan L. S., Li J. W., Ke B. B., Xu Z. K.. Ordered microporous membranes templated by breath figures for size-selective separation[J]. J. Am. Chem. Soc., 2012,134(1):95-98. doi: 10.1021/ja2092745
27. [27]
  Zhu L. W., Ou Y., Wan L. S., Xu Z. K.. Polystyrenes with hydrophilic end groups:synthesis, characterization, and effects on the self-assembly of breath figure arrays[J]. J. Phys. Chem. B, 2014,118(3):845-854. doi: 10.1021/jp4114392
28. [28]
  Chen J. Z., Yan X. Z., Zhao Q. L., Li L., Huang F. H.. Adjustable supramolecular polymer microstructures fabricated by the breath figure method[J]. Polym. Chem., 2012,3(2):458-462. doi: 10.1039/C1PY00438G
29. [29]
  Wang W., Can D., Wang X. F., He X. H., Lin J. P., Li L., Lin S. L.. Directional photomanipulation of breath figure arrays[J]. Angew. Chem. Int. Ed., 2014,53(45):12116-12119. doi: 10.1002/anie.201407230
30. [30]
  Chung Y. T., Ng L. Y., Mohammad A. W.. Sulfonated-polysulfone membrane surface modification by employing methacrylic acid through UV-grafting:optimization through response surface methodology approach[J]. J. Ind. Eng. Chem., 2014,20(4):1549-1557. doi: 10.1016/j.jiec.2013.07.046
31. [31]
  Khoonsap S., Narkkun T., Ratphonsan P., Klinsrisuk S., Mnuaypanich S.. Enhancing the grafting of poly(2-hydroxyethyl methacrylate) on silica nanoparticles (SiO₂-g-PHEMA) by the sequential UV-induced graft polymerization with a multiple-UV irradiation[J]. Adv. Powder Technol., 2014,25(4):1304-1310. doi: 10.1016/j.apt.2014.03.010
32. [32]
  Qin Q., Hou Z. C., Lu X. F., Bian X. K., Chen L. F., Shen L. G., Wang S.. Microfiltration membranes prepared from poly(N-vinyl-2-pyrrolidone) grafted poly(vinylidene fluoride) synthesized by simultaneous irradiation[J]. J. Membr. Sci., 2013,427:303-310. doi: 10.1016/j.memsci.2012.09.059
33. [33]
  Nady N., Schroen K., Franssen M. C. R., Mohy Eldin M. S., Zuilhof H., Boom R. M.. Laccase-catalyzed modification of PES membranes with 4-hydroxybenzoic acid and gallic acid[J]. J. Membr. Sci., 2012,394:69-79.
34. [34]
  Yang M., Xie R., Wang J. Y., Ju X. J., Yang L. H., Chu L. Y.. Gating characteristics of thermo-responsive and molecular-recognizable membranes based on poly (N-isopropylacrylamide) and β-cyclodextrin[J]. J. Membr. Sci., 2010,355(1):142-150.
35. [35]
  Xie R., Zhang S. B., Wang H. D., Yang M., Li P. F., Zhu X. L., Chu L. Y.. Temperature-dependent molecular-recognizable membranes based on poly (N-isopropylacrylamide) and β-cyclodextrin[J]. J. Membr. Sci., 2009,326(2):618-626. doi: 10.1016/j.memsci.2008.10.039
36. [36]
  Yang M., Chu L. Y., Wang H. D., Xie R., Song H., Niu C. H.. A thermoresponsive membrane for chiral resolution[J]. Adv. Funct. Mater., 2008,18(4):652-663. doi: 10.1002/(ISSN)1616-3028
37. [37]
  Schofield W. C. E., Bain C. D., Badyal J. P. S.. Cyclodextrin-functionalized hierarchical porous architectures for high-throughput capture and release of organic pollutants from wastewater[J]. Chem. Mater., 2012,24(9):1645-1653. doi: 10.1021/cm300552k
38. [38]
  Sun H. L., Meng F. H., Cheng R., Deng C., Zhong Z. Y.. Reduction and pH dual-bioresponsive crosslinked polymersomes for efficient intracellular delivery of proteins and potent induction of cancer cell apoptosis[J]. Acta Biomater., 2014,10(5):2159-2168. doi: 10.1016/j.actbio.2014.01.010
39. [39]
  Alsbaiee A., Smith B. J., Xiao L. L., Ling Y. H., Helbling D. E., Dichtel W. R.. Rapid removal of organic micropollutants from water by a porous β-cyclodextrin polymer[J]. Nature, 2016,529(7585):190-194.
40. [40]
  Skey J., O'Reilly R. K.. Facile one pot synthesis of a range of reversible addition-fragmentation chain transfer (RAFT) agents[J]. Chem. Commun., 2008(35):4183-4185. doi: 10.1039/b804260h
41. [41]
  Liu Y. Y., Fan X. D., Gao L.. Synthesis and characterization of β-cyclodextrin based functional monomers and its copolymers with N-isopropylacrylamide[J]. Macromol. Biosci., 2003,3(12):715-719. doi: 10.1002/(ISSN)1616-5195
42. [42]
  Callies M., Quéré D.. On water repellency[J]. Soft Matter, 2005,1(1):55-61. doi: 10.1039/b501657f
43. [43]
  Barthlott W., Neinhuis C.. Purity of the sacred lotus, or escape from contamination in biological surfaces[J]. Planta, 1997,202(1):1-8. doi: 10.1007/s004250050096
44. [44]
  Chatterjee S., Lee M. W., Wooa S. H.. Congo red adsorption from aqueous solutions by using chitosan hydrogel beads impregnated with nonionic or anionic surfactant[J]. Bioresource Technol., 2009,100(17):3862-3868. doi: 10.1016/j.biortech.2009.03.023
45. [45]
  Chabani M., Amrane A., Bensmaili A.. Equilibrium sorption isotherms for nitrate on resin Amberlite IRA 400[J]. J. Hazard. Mater., 2009,165(1):27-33.
46. [46]
  Smith A. E., Xu X. W., Kirkland-York S. E., Savin D. A., McCormick C. L.. "Schizophrenic" self-assembly of block copolymers synthesized via aqueous raft polymerization:from micelles to vesicles[J]. Macromolecules, 2010,43(3):1210-1217. doi: 10.1021/ma902378k
47. [47]
  Mall I. D., Srivastava V. C., Agarwal N. K.. Removal of Orange-G and methyl violet dyes by adsorption onto bagasse fly ash-kinetic study and equilibrium isotherm analyses[J]. Dyes Pigments, 2006,69(3):210-223. doi: 10.1016/j.dyepig.2005.03.013
48. [48]
  Ho Y. S.. Review of second-order models for adsorption systems[J]. J. Hazard. Mater., 2006,136(3):681-689. doi: 10.1016/j.jhazmat.2005.12.043
49. [49]
  Illanes C. O., Ochoa N. A., Marchese J.. Kinetic sorption of Cr(Ⅵ) into solvent impregnated porous microspheres[J]. Chem. Eng. J., 2008,136(2):92-98.
50. [50]
  Xiong L., Yang Y., Mai J., Sun W., Zhang C., Wei D., Chen Q.. Adsorption behavior of methylene blue onto titanate nanotubes[J]. Chem. Eng. J., 2010,156(2):313-320. doi: 10.1016/j.cej.2009.10.023
51. [51]
  Ho Y. S., McKay G.. Pseudo-second order model for sorption processes[J]. Process Biochem., 1999,34(5):451-465. doi: 10.1016/S0032-9592(98)00112-5
1. [1]
  Qinwei Lu , Jinjie Lu , Juying Lei , Xubiao Luo , Yanbo Zhou . Cyclodextrin-boosted photocatalytic oxidation for efficient bisphenol A removal. Chinese Chemical Letters, 2025, 36(3): 110017-. doi: 10.1016/j.cclet.2024.110017
2. [2]
  Yuanpeng Ye , Longfei Yao , Guofeng Liu . Engineering circularly polarized luminescence through symmetry manipulation in achiral tetraphenylpyrazine structures. Chinese Journal of Structural Chemistry, 2025, 44(2): 100460-100460. doi: 10.1016/j.cjsc.2024.100460
3. [3]
  Sifan Du , Yuan Wang , Fulin Wang , Tianyu Wang , Li Zhang , Minghua Liu . Evolution of hollow nanosphere to microtube in the self-assembly of chiral dansyl derivatives and inversed circularly polarized luminescence. Chinese Chemical Letters, 2024, 35(7): 109256-. doi: 10.1016/j.cclet.2023.109256
4. [4]
  Yuwen Zhu , Xiang Deng , Yan Wu , Baode Shen , Lingyu Hang , Yuye Xue , Hailong Yuan . Formation mechanism of herpetrione self-assembled nanoparticles based on pH-driven method. Chinese Chemical Letters, 2025, 36(1): 109733-. doi: 10.1016/j.cclet.2024.109733
5. [5]
  Jingqi Xin , Shupeng Han , Meichen Zheng , Chenfeng Xu , Zhongxi Huang , Bin Wang , Changmin Yu , Feifei An , Yu Ren . A nitroreductase-responsive nanoprobe with homogeneous composition and high loading for preoperative non-invasive tumor imaging and intraoperative guidance. Chinese Chemical Letters, 2024, 35(7): 109165-. doi: 10.1016/j.cclet.2023.109165
6. [6]
  Keyang Li , Yanan Wang , Yatao Xu , Guohua Shi , Sixian Wei , Xue Zhang , Baomei Zhang , Qiang Jia , Huanhua Xu , Liangmin Yu , Jun Wu , Zhiyu He . Flash nanocomplexation (FNC): A new microvolume mixing method for nanomedicine formulation. Chinese Chemical Letters, 2024, 35(10): 109511-. doi: 10.1016/j.cclet.2024.109511
7. [7]
  Xuanyu Wang , Zhao Gao , Wei Tian . Supramolecular confinement effect enabling light-harvesting system for photocatalytic α-oxyamination reaction. Chinese Chemical Letters, 2024, 35(11): 109757-. doi: 10.1016/j.cclet.2024.109757
8. [8]
  Xian Yan , Huawei Xie , Gao Wu , Fang-Xing Xiao . Boosted solar water oxidation steered by atomically precise alloy nanocluster. Chinese Chemical Letters, 2025, 36(1): 110279-. doi: 10.1016/j.cclet.2024.110279
9. [9]
  Feng Cao , Chunxiang Xian , Tianqi Yang , Yue Zhang , Haifeng Chen , Xinping He , Xukun Qian , Shenghui Shen , Yang Xia , Wenkui Zhang , Xinhui Xia . Gelation-pyrolysis strategy for fabrication of advanced carbon/sulfur cathodes for lithium-sulfur batteries. Chinese Chemical Letters, 2025, 36(3): 110575-. doi: 10.1016/j.cclet.2024.110575
10. [10]
  Changlin Su , Wensheng Cai , Xueguang Shao . Water as a probe for the temperature-induced self-assembly transition of an amphiphilic copolymer. Chinese Chemical Letters, 2025, 36(4): 110095-. doi: 10.1016/j.cclet.2024.110095
11. [11]
  Siwei Wang , Wei-Lei Zhou , Yong Chen . Cucurbituril and cyclodextrin co-confinement-based multilevel assembly for single-molecule phosphorescence resonance energy transfer behavior. Chinese Chemical Letters, 2024, 35(12): 110261-. doi: 10.1016/j.cclet.2024.110261
12. [12]
  Zhenzhu Wang , Chenglong Liu , Yunpeng Ge , Wencan Li , Chenyang Zhang , Bing Yang , Shizhong Mao , Zeyuan Dong . Differentiated self-assembly through orthogonal noncovalent interactions towards the synthesis of two-dimensional woven supramolecular polymers. Chinese Chemical Letters, 2024, 35(5): 109127-. doi: 10.1016/j.cclet.2023.109127
13. [13]
  Cheng-Yan Wu , Yi-Nan Gao , Zi-Han Zhang , Rui Liu , Quan Tang , Zhong-Lin Lu . Enhancing self-assembly efficiency of macrocyclic compound into nanotubes by introducing double peptide linkages. Chinese Chemical Letters, 2024, 35(11): 109649-. doi: 10.1016/j.cclet.2024.109649
14. [14]
  Xiaofei NIU , Ke WANG , Fengyan SONG , Shuyan YU . Self-assembly of [Pd₆(L)₄]⁸⁺-type macrocyclic complexes for fluorescent sensing of HSO₃^-. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1233-1242. doi: 10.11862/CJIC.20240057
15. [15]
  Zengchao Guo , Weiwei Liu , Tengfei Liu , Jinpeng Wang , Hui Jiang , Xiaohui Liu , Yossi Weizmann , Xuemei Wang . Engineered exosome hybrid copper nanoscale antibiotics facilitate simultaneous self-assembly imaging and elimination of intracellular multidrug-resistant superbugs. Chinese Chemical Letters, 2024, 35(7): 109060-. doi: 10.1016/j.cclet.2023.109060
16. [16]
  Jin Tong , Shuyan Yu . Crystal Engineering for Supramolecular Chirality. University Chemistry, 2024, 39(3): 86-93. doi: 10.3866/PKU.DXHX202308113
17. [17]
  Ruoxi Sun , Yiqian Xu , Shaoru Rong , Chunmiao Han , Hui Xu . The Enchanting Collision of Light and Time Magic: Exploring the Footprints of Long Afterglow Lifetime. University Chemistry, 2024, 39(5): 90-97. doi: 10.3866/PKU.DXHX202310001
18. [18]
  Changhui Yu , Peng Shang , Huihui Hu , Yuening Zhang , Xujin Qin , Linyu Han , Caihe Liu , Xiaohan Liu , Minghua Liu , Yuan Guo , Zhen Zhang . Evolution of template-assisted two-dimensional porphyrin chiral grating structure by directed self-assembly using chiral second harmonic generation microscopy. Chinese Chemical Letters, 2024, 35(10): 109805-. doi: 10.1016/j.cclet.2024.109805
19. [19]
  Bing Niu , Honggao Huang , Liwei Luo , Li Zhang , Jianbo Tan . Coating colloidal particles with a well-defined polymer layer by surface-initiated photoinduced polymerization-induced self-assembly and the subsequent seeded polymerization. Chinese Chemical Letters, 2025, 36(2): 110431-. doi: 10.1016/j.cclet.2024.110431
20. [20]
  Yi Zhou , Wei Zhang , Rong Fu , Jiaxin Dong , Yuxuan Liu , Zihang Song , Han Han , Kang Cai . Self-assembly of two pairs of homochiral M₂L₄ coordination capsules with varied confined space using Tröger's base ligands. Chinese Chemical Letters, 2025, 36(2): 109865-. doi: 10.1016/j.cclet.2024.109865

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(856)
HTML views(52)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142