N-异丙基丙烯酰胺嵌段共聚物自组装行为研究进展

doi:10.11949/j.issn.0438-1157.20160755

摘要/Abstract

摘要：

具有两亲性和温敏性的嵌段共聚物在选择性溶剂中能够自组装形成独特的微米级甚至纳米级有序结构，具有广泛的潜在应用。聚N-异丙基丙烯酰胺（PNIPAM）是一种典型的温敏性高分子材料，其分子链表现出独特的温敏行为，关于其修饰改性以及自组装行为的研究一直广受关注。以PNIPAM为基点介绍其嵌段共聚物的自组装行为，详细综述影响其行为的诸多因素如组成、分子量、外界刺激条件等，介绍其在生物医药、催化反应等方面的应用，并对其未来的发展方向进行了展望。

关键词: 聚合物, PNIPAM, 两亲性, 选择性, 纳米粒子

Abstract:

The amphiphilic and thermosensitive block copolymers can self-assemble and turn into special micron level or nanoscale morphologies in selective solvents, and they have extensive potential applications. Poly(N-isopropyl acrylamide) (PNIPAM) is a typical kind of thermal-sensitive macromolecular material. It can undergo a special “coil to globule” volume phase transition near the lower critical solution temperature in solution. The study of self-assembly of its block copolymers has been drawn great interests. In this paper, self-assembly of PNIPAM block copolymers is introduced. The influence of several aspects including composition, molecular weight, external stimulus conditions and so on is systematically reviewed. Some of its applications on biological medicine, catalysis reaction, etc. are also introduced. The direction of its future development is also forecasted.

Key words: polymers, PNIPAM, amphiphilic, selectivity, nanoparticles

中图分类号:

TQ326.4

赵小燕, 单国荣. N-异丙基丙烯酰胺嵌段共聚物自组装行为研究进展[J]. 化工学报, 2017, 68(2): 535-541.

ZHAO Xiaoyan, SHAN Guorong. Research progress on self-assembly of block copolymers of N-isopropyl acrylamide[J]. CIESC Journal, 2017, 68(2): 535-541.

参考文献 32

[1]	LI X Y, GAO Y, BOOTT C E, et al. "Cross" supermicelles via the hierarchical assembly of amphiphilic cylindrical triblock comicelles[J]. Journal of the American Chemical Society, 2016, 138(12):4087-4095.
[2]	THOMAS E L, ANDERSON D M, HENKEE C S, et al. Periodic area-minimizing surfaces in block copolymers[J]. Nature, 1988, 334(6183):598-601.
[3]	BATES F S. Polymer-polymer phase-behavior[J]. Science, 1991, 251(4996):898-905.
[4]	MAI Y Y, EISENBERG A. Self-assembly of block copolymers[J]. Chemical Society Reviews, 2012, 41(18):5969-5985.
[5]	FONG C, Le T, DRUMMOND C J. Lyotropic liquid crystal engineering-ordered nanostructured small molecule amphiphile self-assembly materials by design[J]. Chemical Society Reviews, 2012, 41(3):1297-1322.
[6]	YAO C, LIU Z, YANG C, et al. Poly(N-isopropylacrylamide)-clay nanocomposite hydrogels with responsive bending property as temperature-controlled manipulators[J]. Advanced Functional Materials, 2015, 25(20):2980-2991.
[7]	WANG W, GAO C Q, QU Y Q, et al. In situ synthesis of thermoresponsive polystyrene-b-poly(N-isopropylacrylamide)-bpolystyrene nanospheres and comparative study of the looped and linear poly(N-isopropylacrylamide)s[J]. Macromolecules, 2016, 49(7):2772-2781.
[8]	CAO Z H, ZIENER U, LANDFESTER K. Synthesis of narrowly size-distributed thermosensitive poly(N-isopropylacrylamide) nanocapsules in inverse miniemulsion[J]. Macromolecules, 2010, 43(15):6353-6360.
[9]	LI S Y, LIN D L, ZHOU J F, et al. Preparation of silver nanoparticles loaded photoresponsive composite microgels and their lightcontrollable catalytic activity[J]. Journal of Physical Chemistry C, 2016, 120(9):4902-4908.
[10]	BAJPAI A K, SHUKLA S K, BHANU S, et al. Responsive polymers in controlled drug delivery[J]. Progress in Polymer Science, 2008, 33(11):1088-1118.
[11]	WU C, WANG X H. Globule-to-coil transition of a single homopolymer chain in solution[J]. Physical Review Letters, 1998, 80(18):4092-4094.
[12]	RZAEV Z M O, DINCER S, PISKIN E. Functional copolymers of N-isopropylacrylamide for bioengineering applications[J]. Progress in Polymer Science, 2007, 32(5):534-595.
[13]	SCARPA J S, MUELLER D D, KLOTZ I M. Slow hydrogendeuterium exchange in a non-alpha-helical polyamide[J]. Journal of the American Chemical Society, 1967, 89(24):6024-6030.
[14]	DIMITROV I, TRZEBICKA B, MULLER A H E, et al. Thermosensitive water-soluble copolymers with doubly responsive reversibly interacting entities[J]. Progress in Polymer Science, 2007, 32(11):1275-1343.
[15]	SERPE M J, JONES C D, LYON L A. Layer-by-layer deposition of thermoresponsive microgel thin films[J]. Langmuir, 2003, 19(21):8759-8764.
[16]	GE Z S, LUO S Z, LIU S Y. Syntheses and self-assembly of poly(benzyl ether)-b-poly(N-isopropylacrylamide) dendritic-linear diblock copolymers[J]. Journal of Polymer Science Part A-Polymer Chemistry, 2006, 44(4):1357-1371.
[17]	NYKANEN A, NUOPPONEN M, LAUKKANEN A, et al. Phase behavior and temperature-responsive molecular filters based on self-assembly of polystyrene-block-poly(N-isopropylacrylamide)-block-polystyrene[J]. Macromolecules, 2007, 40(16):5827-5834.
[18]	QIN S H, GENG Y, DISCHER D E, et al. Temperature-controlled assembly and release from polymer vesicles of poly(ethylene oxide)-block-poly(N-isopropylacrylamide)[J]. Advanced Materials, 2006, 18(21):2905-2909.
[19]	GAN D J, LYON L A. Fluorescence nonradiative energy transfer analysis of crosslinker heterogeneity in core-shell hydrogel nanoparticles[J]. Analytica Chimica Acta, 2003, 496(1-2):53-63.
[20]	JOCHUM F D, THEATO P. Thermo-and light responsive micellation of azobenzene containing block copolymers[J]. Chemical Communications, 2010, 46(36):6717-6719.
[21]	艾长军, 唐燕春, 张莉, 等. 聚(甲基)丙烯酸叔丁酯-b-聚(N-异丙基丙烯酰胺)嵌段共聚物的ATRP法合成及其自组装行为[J]. 材料导报, 2010, 25(S1):408-411. AI C J, TANG Y C, ZHANG L, et al. Synthesis of poly(tert-butyl(meth)acrylate)-b-poly(N-isopropyl acrylamide) by atom transfer radical polymerization and their self-assembly behavior[J]. Materials Review, 2010, 25(S1):408-411.
[22]	CHANG C, WEI H, QUAN C Y, et al. Fabrication of thermosensitive PCL-PNIPAAm-PCL triblock copolymeric micelles for drug delivery[J]. Journal of Polymer Science Part A-Polymer Chemistry, 2008, 46(9):3048-3057.
[23]	PRAMANIK P, GHOSH S. Thermoresponsive polymersome from a double hydrophilic block copolymer[J]. Journal of Polymer Science Part A-Polymer Chemistry, 2015, 53(21):2444-2451.
[24]	MÄKINEN L, VARADHARAJAN D, TENHU H, et al. Triple hydrophilic UCST-LCST block copolymers[J]. Macromolecules, 2016, 49(3):986-993.
[25]	KLAIKHERD A, NAGAMANI C, THAYUMANAVAN S. Multi-stimuli sensitive amphiphilic block copolymer assemblies[J]. Journal of the American Chemical Society, 2009, 131(13):4830-4838.
[26]	AHMED F, PAKUNLU R I, BRANNAN A, et al. Biodegradable polymersomes loaded with both paclitaxel and doxorubicin permeate and shrink tumors, inducing apoptosis in proportion to accumulated drug[J]. Journal of Controlled Release, 2006, 116(2):150-158.
[27]	BROZ P, DRIAMOV S, ZIEGLER J, et al. Toward intelligent nanosize bioreactors:a pH-switchable, channel-equipped, functional polymer nanocontainer[J]. Nano Letters, 2006, 6(10):2349-2353.
[28]	LOMAS H, CANTON I, MACNEIL S, et al. Biomimetic pH sensitive polymersomes for efficient DNA encapsulation and delivery[J]. Advanced Materials, 2007, 19(23):4238-4243.
[29]	MAI Y, EISENBERG A. Controlled incorporation of particles into the central portion of vesicle walls[J]. Journal of the American Chemical Society, 2010, 132(29):10078-10084.
[30]	WEI H, ZHANG X Z, ZHOU Y, et al. Self-assembled thermoresponsive micelles of poly(N-isopropylacrylamide-b-methyl methacrylate)[J]. Biomaterials, 2006, 27(9):2028-2034.
[31]	URBANI C N, MONTEIRO M J. RAFT-mediated emulsion polymerization of styrene in water using a reactive polymer nanoreactor[J]. Australian Journal of Chemistry, 2009, 62(11):1528-1532.
[32]	VALADE D, JEON Y, KESSEL S, et al. Influence of the Z-group on the RAFT-mediated polymerizations in nanoreactors[J]. Journal of Polymer Science Part A-Polymer Chemistry, 2012, 50(22):4762-4771.OU J F,et al.Preparation of silver nanoparticles loaded photoresponsive composite microgels and their light-controllable catalytic activity[J].Journal of Physical Chemistry C,2016,120(9):4902-4908.
[10]	BAJPAI A K,SHUKLA S K,BHANU S,et al.Responsive polymers in controlled drug delivery[J].Progress in Polymer Science,2008,33(11):1088-1118.
[11]	WU C,WANG X H.Globule-to-coil transition of a single homopolymer chain in solution[J].Physical Review Letters,1998,80(18):4092-4094.
[12]	RZAEV Z M O,DINCER S,PISKIN E.Functional copolymers of N-isopropylacrylamide for bioengineering applications[J].Progress in Polymer Science,2007,32(5):534-595.
[13]	SCARPA J S,MUELLER D D,KLOTZ I M.Slow hydrogen-deuterium exchange in a non-alpha-helical polyamide[J].Journal of the American Chemical Society,1967,89(24):6024-6030.
[14]	DIMITROV I,TRZEBICKA B,MULLER A H E,et al.Thermosensitive water-soluble copolymers with doubly responsive reversibly interacting entities[J].Progress in Polymer Science,2007,32(11):1275-1343.
[15]	SERPE M J,JONES C D,LYON L A.Layer-by-layer deposition of thermoresponsive microgel thin films[J].Langmuir,2003,19(21):8759-8764.
[16]	GE Z S,LUO S Z,LIU S Y.Syntheses and self-assembly of poly (benzyl ether)-b-poly (N-isopropylacrylamide) dendritic-linear diblock copolymers[J].Journal of Polymer Science Part a-Polymer Chemistry,2006,44(4):1357-1371.
[17]	NYKANEN A,NUOPPONEN M,LAUKKANEN A,et al.Phase behavior and temperature-responsive molecular filters based on self-assembly of polystyrene-block-poly (N-isopropylacrylamide)-block-polystyrene[J].Macromolecules,2007,40(16):5827-5834.
[18]	QIN S H,GENG Y,DISCHER D E,et al.Temperature-controlled assembly and release from polymer vesicles of poly (ethylene oxide)-block-poly (N-isopropylacrylamide)[J].Advanced Materials,2006,18(21):2905-2909.
[19]	GAN D J,LYON L A.Fluorescence nonradiative energy transfer analysis of crosslinker heterogeneity in core-shell hydrogel nanoparticles[J].Analytica Chimica Acta,2003,496(1-2):53-63.
[20]	JOCHUM F D,THEATO P.Thermo-and light responsive micellation of azobenzene containing block copolymers[J].Chemical Communications,2010,46(36):6717-6719.
[21]	艾长军,唐燕春,张莉,等.聚(甲基)丙烯酸叔丁酯-b-聚(N-异丙基丙烯酰胺)嵌段共聚物的ATRP法合成及其自组装行为[J].材料导报,2010,25(S1):408-411.AI C J,TANG Y C,ZHANG L,et al.Synthesis of poly (tert-butyl (meth) acrylate)-b-poly (N-isopropyl acrylamide) by atom transfer radical polymerization and their self-assembly behavior[J].Materials Review,2010,25(S1):408-411.
[22]	CHANG C,WEI H,QUAN C Y,et al.Fabrication of thermosensitive PCL-PNIPAAm-PCL triblock copolymeric micelles for drug delivery[J].Journal of Polymer Science Part a-Polymer Chemistry,2008,46(9):3048-3057.
[23]	PRAMANIK P,GHOSH S.Thermoresponsive polymersome from a double hydrophilic block copolymer[J].Journal of Polymer Science Part a-Polymer Chemistry,2015,53(21):2444-2451.
[24]	MAKINEN L,VARADHARAJAN D,TENHU H,et al.Triple hydrophilic UCST-LCST block copolymers[J].Macromolecules,2016,49(3):986-993.
[25]	KLAIKHERD A,NAGAMANI C,THAYUMANAVAN S.Multi-Stimuli Sensitive Amphiphilic Block Copolymer Assemblies[J].Journal of the American Chemical Society,2009,131(13):4830-4838.
[26]	AHMED F,PAKUNLU R I,BRANNAN A,et al.Biodegradable polymersomes loaded with both paclitaxel and doxorubicin permeate and shrink tumors,inducing apoptosis in proportion to accumulated drug[J].Journal of Controlled Release,2006,116(2):150-158.
[27]	BROZ P,DRIAMOV S,ZIEGLER J,et al.Toward intelligent nanosize bioreactors:A pH-switchable,channel-equipped,functional polymer nanocontainer[J].Nano Letters,2006,6(10):2349-2353.
[28]	LOMAS H,CANTON I,MACNEIL S,et al.Biomimetic pH sensitive polymersomes for efficient DNA encapsulation and delivery[J].Advanced Materials,2007,19(23):4238-4243.
[29]	MAI Y,EISENBERG A.Controlled incorporation of particles into the central portion of vesicle walls[J].Journal of the American Chemical Society,2010,132(29):10078-10084.
[30]	WEI H,ZHANG X Z,ZHOU Y,et al.Self-assembled thermoresponsive micelles of poly (N-isopropylacrylamide-b-methyl methacrylate)[J].Biomaterials,2006,27(9):2028-2034.
[31]	URBANI C N,MONTEIRO M J.RAFT-mediated emulsion polymerization of styrene in water using a reactive polymer nanoreactor[J].Australian Journal of Chemistry,2009,62(11):1528-1532.
[32]	VALADE D,JEON Y,KESSEL S,et al.Influence of the Z-group on the RAFT-mediated polymerizations in nanoreactors[J].Journal of Polymer Science Part a-Polymer Chemistry,2012,50(22):4762-4771.

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