PSSS50-b-PNIPAM300嵌段共聚物在二元溶剂中自组装的NMR研究

doi:10.11938/cjmr20192736

波谱学杂志 ›› 2019, Vol. 36 ›› Issue (4): 502-509.doi: 10.11938/cjmr20192736

PSSS₅₀-b-PNIPAM₃₀₀嵌段共聚物在二元溶剂中自组装的NMR研究

赵智慧^1,2, 刘表兰¹, 闫小双^1,2, 武帅帅^1,2, 茹阁英¹, 毛诗珍¹, 冯继文¹

1. 波谱与原子分子物理国家重点实验室, 武汉磁共振中心(中国科学院武汉物理与数学研究所), 湖北武汉 430071;
2. 中国科学院大学, 北京 100049

收稿日期:2019-04-12 出版日期:2019-12-05 发布日期:2019-05-30
通讯作者: 刘表兰, 毛诗珍, 冯继文 E-mail:blliu@wipm.ac.cn;maosz@wipm.ac.cn;jwfeng@wipm.ac.cn
基金资助:
国家自然科学基金资助项目（21803076）.

Thermally Triggered Self-Assembly of PSSS₅₀-b-PNIPAM₃₀₀ in Binary Solvent Studied by NMR Spectroscopy

ZHAO Zhi-hui^1,2, LIU Biao-lan¹, YAN Xiao-shuang^1,2, WU Shuai-shuai^1,2, RU Ge-ying¹, MAO Shi-zhen¹, Feng Ji-wen¹

1. State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, National Center for Magnetic Resonance in Wuhan(Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences), Wuhan 430071, China;
2. University of Chinese Academy of Sciences, Beijing 100049, China

Received:2019-04-12 Online:2019-12-05 Published:2019-05-30

摘要/Abstract

摘要： 本文结合核磁共振（NMR）、动态光散射（DLS）和透射电子显微镜（TEM）等表征方法，对自主合成的聚阴离子型温敏嵌段共聚物—聚（苯乙烯磺酸钠）-b-聚（N-异丙基丙烯酰胺）（PSSS₅₀-b-PNIPAM₃₀₀）在纯水、水/甲醇以及水/丙酮三种溶剂中的温度响应性和自组装行为进行了系统研究.结果发现PNIPAM链段在水/丙酮以及水/甲醇二元溶剂中的临界溶解温度（LCST）比在纯水溶液中略低，而在水/丙酮体系中的塌缩程度却明显低于纯水和水/甲醇体系.同时，PSSS₅₀-b-PNIPAM₃₀₀在不同溶剂体系中的聚集形貌也存在显著差异，表明加入有机溶剂小分子可以有效地调控温敏嵌段共聚物在水溶液中的自组装过程和聚集形貌.

关键词: 核磁共振(NMR), 自组装, 嵌段共聚物, 二元溶剂, 温度响应性

Abstract: Thermo-responsiveness and self-assembly behaviors of poly(sodium-p-styrene sulfonate)-block-poly (N-isopropylacrylamide) (PSSS₅₀-b-PNIPAM₃₀₀) in pure water and binary solvents (i.e., water/methanol and water/acetone) were investigated by ¹H NMR, dynamic light scattering (DLS), and transmission electron microscopy (TEM). It was found that the PNIPAM chains had a lower lowest critical solution temperature (LCST) in the water/methanol and water/acetone binary solvents than in water. Temperature-induced collapse of PNIPAM in water/acetone binary solvent was evidently weaker compared to the collapses in pure water and water/methanol binary solvent. The DLS and TEM results demonstrated that the self-assembly process and morphology of PSSS₅₀-b-PNIPAM₃₀₀ in aqueous solution could be fine-tuned with the addition of small molecule solvent.

Key words: nuclear magnetic resonance (NMR), self-assembly, block copolymer, binary solvent, thermo-sensitivity

中图分类号:

O482.53

赵智慧, 刘表兰, 闫小双, 武帅帅, 茹阁英, 毛诗珍, 冯继文. PSSS₅₀-b-PNIPAM₃₀₀嵌段共聚物在二元溶剂中自组装的NMR研究[J]. 波谱学杂志, 2019, 36(4): 502-509.

ZHAO Zhi-hui, LIU Biao-lan, YAN Xiao-shuang, WU Shuai-shuai, RU Ge-ying, MAO Shi-zhen, Feng Ji-wen. Thermally Triggered Self-Assembly of PSSS₅₀-b-PNIPAM₃₀₀ in Binary Solvent Studied by NMR Spectroscopy[J]. Chinese Journal of Magnetic Resonance, 2019, 36(4): 502-509.

参考文献

[1] SCHILD H G. Poly(N-isopropylacrylamide):experiment, theory and application[J]. Prog Polym Sci, 1992, 17(2):163-249.
[2] SCHILD H G, MUTHUKUMAR M, TIRRELL D A. Cononsolvency in mixed aqueous solutions of poly(N-isopropylacrylamide)[J]. Macromolecules, 1991, 24(4):948-952.
[3] COSTA R O R, FREITAS R F S. Phase behavior of poly(N-isopropylacrylamide) in binary aqueous solutions[J]. Polymer, 2002, 43(22):5879-5885.
[4] WANG N, RU G Y, WANG L Y, et al. ¹H MAS NMR studies of the phase separation of poly(N-isopropylacrylamide) gel in binary solvents[J]. Langmuir, 2009, 25(10):5898-5902.
[5] LIU B L, WANG J, RU G Y, et al. Phase transition and preferential alcohol adsorption of poly(N, N-diethylacrylamide) gel in water/alcohol mixtures[J]. Macromolecules, 2015, 48(4):1126-1133.
[6] WANG J, LIU B L, RU G Y, et al. Effect of urea on phase transition of poly(N-isopropylacrylamide) and poly(N, N-diethylacrylamide) hydrogels:a clue for urea-induced denaturation[J]. Macromolecules, 2016, 49(1):234-243.
[7] WANG J, WANG N, LIU B L, et al. Preferential adsorption of the additive is not a prerequisite for cononsolvency in water-rich mixtures[J]. Phys Chem Chem Phys, 2017, 19(44):30097-30106.
[8] GAN D J, LYON L A. Tunable swelling kinetics in core-shell hydrogel nanoparticles[J]. J Am Chem Soc, 2001, 123(31):7511-7517.
[9] WANG D, WU T, WAN X J, et al. Purely salt-responsive micelle formation and inversion based on a novel schizophrenic sulfobetaine block copolymer: structure and kinetics of micellization[J]. Langmuir, 2007, 23(23):11866-11874.
[10] HUANG C J, CHANG F C. Polypeptide diblock copolymers:syntheses and properties of poly(N-isopropylacrylamide)-b-polylysine[J]. Macromolecules, 2008, 41(19):7041-7052.
[11] WEI H, CHENG S X, ZHANG X Z, et al. Thermo-sensitive polymeric micelles based on poly(N-isopropylacrylamide) as drug carriers[J]. Prog Polym Sci, 2009, 34(9):893-910.
[12] RöSLER A, VANDERMEULEN G W M, KLOK H A. Advanced drug delivery devices via self-assembly of amphiphilic block copolymers[J]. Adv Drug Deliv Rev, 2001, 53(1):95-108.
[13] WANG S, ZHANG Z F, ZHANG Q H, et al. Physical crosslinked poly(N-isopropylacrylamide)/nano-hydroxyapatite thermosensitive composite hydrogels[J]. J Inorg Organomet P, 2018, 28(5):2069-2079.
[14] CHEN Y, ZHOU Y Y, LIU W Y, et al. POSS hybrid robust biomass ipn hydrogels with temperature responsiveness[J]. Polymers, 2019, 11(3):524.
[15] KANTO R, QIAO Y H, MASUKO K, et al. Synthesis, assembled structures, and DNA complexation of thermoresponsive lysine-based zwitterionic and cationic block copolymers[J]. Langmuir, 2019, 35(13):4646-4659.
[16] LU Y, ZHENG X W, ZHONG K. Research progresses in development of thermo-sensitive mri contrast agent[J]. Chinese J Magn Reson, 2017, 34(4):528-536. 路遥, 郑新威, 钟凯. 温敏性磁共振成像造影剂的研究进展[J]. 波谱学杂志, 2017, 34(4):528-536.
[17] GAN D J, LYON L A. Fluorescence nonradiative energy transfer analysis of crosslinker heterogeneity in core-shell hydrogel nanoparticles[J]. Anal Chim Acta, 2003, 496(1):53-63.
[18] JOCHUM F D, THEATO P. Thermo- and light responsive micellation of azobenzene containing block copolymers[J]. Chem Commun, 2010, 46(36):6717-6719.
[19] QIN S, GENG Y, DISCHER D E, et al. Temperature-controlled assembly and release from polymer vesicles of poly(ethylene oxide)-block-poly(N-isopropylacrylamide)[J]. Adv Mater, 2006, 18(21):2905-2909.
[20] 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.
[21] GE Z Z, LUO S Z, LIU S Y. Syntheses and self-assembly of poly(benzyl ether)-b-poly(N-isopropylacrylamide) dendritic-linear diblock copolymers[J]. J Polym Sci Pol Chem, 2006, 44(4):1357-1371.
[22] NYKäNEN 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.
[23] PRAMANIK P, GHOSH S. Thermoresponsive polymersome from a double hydrophilic block copolymer[J]. J Polym Sci Pol Chem, 2015, 53(21):2444-2451.
[24] LIU B L, WANG J, ZHANG Y, et al. Inhomogeneous-collapse driven micelle-vesicle transition of amphiphilic block copolymers[J]. Soft Matter, 2017, 13(39):7106-7111.
[25] FENG A C, ZHAN C B, YAN Q, et al. A CO₂- and temperature-switchable "schizophrenic" block copolymer:from vesicles to micelles[J]. Chem Commun, 2014, 50(64):8958-8961.
[26] YAN Q, ZHAO Y. CO₂-stimulated diversiform deformations of polymer assemblies[J]. J Am Chem Soc, 2013, 135(44):16300-16303.
[27] WARREN N J, ARMES S P. Polymerization-induced self-assembly of block copolymer nano-objects via RAFT aqueous dispersion polymerization[J]. J Am Chem Soc, 2014, 136(29):10174-10185.
[28] ZHOU W, QU Q W, XU Y Y, et al. Aqueous polymerization-induced self-assembly for the synthesis of ketone-functionalized nano-objects with low polydispersity[J]. ACS Macro Lett, 2015, 4(5):495-499.
[29] MABLE C J, FIELDING L A, DERRY M J, et al. Synthesis and pH-responsive dissociation of framboidal ABC triblock copolymer vesicles in aqueous solution[J]. Chem Sci, 2018, 9(6):1454-1463.
[30] WANG N, RU G Y, WANG L Y, et al. NMR studies on phase separation of linear PNIPAM and gel in binary solvents[J]. Chinese J Magn Reson, 2010, 27(3):461-469. 王念, 茹阁英, 王立英, 等. PNIPAM线性链与凝胶在二元溶剂中相变的变温NMR研究[J]. 波谱学杂志, 2010, 27(3):461-469.
[31] 王念. 二元溶剂中聚(N-异丙基丙烯酰胺)相变的NMR研究[D]. 武汉:中国科学院武汉物理与数学研究所, 2009.

PSSS₅₀-b-PNIPAM₃₀₀嵌段共聚物在二元溶剂中自组装的NMR研究

Thermally Triggered Self-Assembly of PSSS₅₀-b-PNIPAM₃₀₀ in Binary Solvent Studied by NMR Spectroscopy

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