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清华大学化学工程系高分子研究所 北京 100084
E-mail: yangzhenzhong@mail.tsinghua.edu.cn
纸质出版日期:2025-01-20,
网络出版日期:2024-11-15,
收稿日期:2024-06-19,
录用日期:2024-09-11
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李枫霖, 杨雅静, 孙大吟, 叶一兰, 杨振忠. 规模制备Janus聚合物单链@纳米颗粒杂化体. 高分子学报, 2025, 56(1), 114-123
Li, F. L.; Yang, Y. J.; Sun, D. Y.; Ye, Y. L.; Yang, Z. Z. Scalable synthesis of Janus single-chain/nanoparticle hybrids. Acta Polymerica Sinica, 2025, 56(1), 114-123
李枫霖, 杨雅静, 孙大吟, 叶一兰, 杨振忠. 规模制备Janus聚合物单链@纳米颗粒杂化体. 高分子学报, 2025, 56(1), 114-123 DOI: 10.11777/j.issn1000-3304.2024.24173. CSTR: 32057.14.GFZXB.2024.7282.
Li, F. L.; Yang, Y. J.; Sun, D. Y.; Ye, Y. L.; Yang, Z. Z. Scalable synthesis of Janus single-chain/nanoparticle hybrids. Acta Polymerica Sinica, 2025, 56(1), 114-123 DOI: 10.11777/j.issn1000-3304.2024.24173. CSTR: 32057.14.GFZXB.2024.7282.
非对称Janus聚合物单链与纳米颗粒杂化体系具有精细结构及功能耦合特性,其规模制备具有重要意义. 以三嵌段瓶刷聚合物为基础,基于静电介导单链分子内交联方法同时实现Fe
3
O
4
原位负载,规模合成了Janus纳米复合颗粒,最高合成浓度达150 mg/mL. 该复合颗粒两侧的聚合物链可分别改性获得官能团,为组装和荧光染色观察提供了条件. 在纳米复合颗粒表面通过溶胶-凝胶反应包覆SiO
2
并引入溴丙基,为终止活性阴离子聚合物提供位点. 基于空间位阻效应,可在纳米复合颗粒表面顺次键接两根活性阴离子聚合物链,其结构与组成可控,获得了表面具有4根不同聚合物单链的多价态Janus聚合物单链@纳米颗粒功能杂化体,为组装构筑超结构提供重要材料.
Asymmetric polymer single-chain@nanoparticle hybrids demonstrate fine microstructures and synergetic performances
which serve as important building blocks toward functional materials. It is crucial to develop methodologies for the large-scale preparation of hierarchically structured
functional hybrids. Starting from the triblock bottlebrush polymers
Janus nanoparticles composed of Fe
3
O
4
are synthesized on a large scale through electrostatic-mediated intramolecular crosslinking
involving coordination with metallic ions at the central region
which is rich in PVP side chains at a high concentration of 150 mg/mL. Shape of the nanoparticles is controllable from spherical to ellipsoidal by alteration of the length ratio of the backbone and the grafting side chain. PVSt and PBBzSt blocks at the opposite ends of the nanoparticle could be modified orthogonally to derive amino- or (and) carboxylic acid groups. AB type Janus nanoparticles are thus derived
which are able to self-assembly into diverge superstructures upon alteration of pH values. The self-assembly and the superstructures could be easily visualized under stimulated emission depletion microscope (STED) upon fluorescent dyeing the functional groups. A layer of SiO
2
is formed at the Fe
3
O
4
NP by the sol-gel process
and bromopropyl- groups are further introduced by using the silane. At the Janus composite nanoparticle
single-chains could be sequentially grafted by steric hindrance assisted termination of living anionic polymer single-chains with tunable composition and microstructure. The Janus composite nanoparticles bearing four different polymer chains display multivalent directional interactions
which are promising to self-assembly functional superstructures.
瓶刷聚合物静电介导分子内交联Janus纳米复合颗粒
Bottlebrush polymerElectrostatics-mediatedIntramolecular cross-linkingJanusHybrid nanoparticle
Shao Y.; Yang Z. Z.Progress in polymer single-chain based hybrid nanoparticles. Prog. Polym. Sci., 2022, 133, 101593. doi:10.1016/j.progpolymsci.2022.101593http://dx.doi.org/10.1016/j.progpolymsci.2022.101593
叶一兰, 孙大吟, 杨振忠. 高分子单链-胶体杂化纳米颗粒的合成进展与挑战. 高分子学报, 2022, 53(12), 1429-1444. doi:10.11777/j.issn1000-3304.2022.22177http://dx.doi.org/10.11777/j.issn1000-3304.2022.22177
Xiang D.; Chen X.; Tang L.; Jiang B. Y.; Yang Z. Z.Electrostatic-mediated intramolecular cross-linking polymers in concentrated solutions. CCS Chem., 2019, 1(5), 407-430. doi:10.31635/ccschem.019.20190035http://dx.doi.org/10.31635/ccschem.019.20190035
Lang F. Z.; Xiang D.; Wang J. W.; Yang L. P.; Qiao Y.; Yang Z. Z.Janus colloidal dimer by intramolecular cross-linking in concentrated solutions. Macromolecules, 2020, 53(6), 2271-2278. doi:10.1021/acs.macromol.0c00180http://dx.doi.org/10.1021/acs.macromol.0c00180
Wang J. W.; Chen X.; Lang F. Z.; Yang L. P.; Qiu D.; Yang Z. Z.Large scale synthesis of single-chain/colloid Janus nanoparticles with tunable composition. Chem. Commun., 2020, 56(27), 3875-3878. doi:10.1039/d0cc00686fhttp://dx.doi.org/10.1039/d0cc00686f
Xiang D.; Jiang B. Y.; Liang F. X.; Yan L. T.; Yang Z. Z.Single-chain Janus nanoparticle by metallic complexation. Macromolecules, 2020, 53(3), 1063-1069. doi:10.1021/acs.macromol.9b02388http://dx.doi.org/10.1021/acs.macromol.9b02388
Xu W.; Ye Y. L.; Sun D. Y.; Yang Z. Z.Single-chain nanoparticle catalyzed polymerization toward composite nanoparticles. J. Polym. Sci., 2024, 62(3), 427-435. doi:10.1002/pol.20230379http://dx.doi.org/10.1002/pol.20230379
Yao X. H.; Jing J. Y.; Liang F. X.; Yang Z. Z.Polymer-Fe3O4 composite Janus nanoparticles. Macromolecules, 2016, 49(24), 9618-9625. doi:10.1021/acs.macromol.6b02004http://dx.doi.org/10.1021/acs.macromol.6b02004
Yang Y. J.; Li F. L.; Sun D. Y.; Ye Y. L.; Yang Z. Z.Large-scale synthesis of reactive Janus inorganic/polymer colloidal dimer. Macromolecules, 2024, 57(3), 880-886. doi:10.1021/acs.macromol.3c02334http://dx.doi.org/10.1021/acs.macromol.3c02334
Müllner M.; Müller A. H. E.Cylindrical polymer brushes-anisotropic building blocks, unimolecular templates and particulate nanocarriers. Polymer, 2016, 98, 389-401. doi:10.1016/j.polymer.2016.03.076http://dx.doi.org/10.1016/j.polymer.2016.03.076
Lee H. I.; Pietrasik J.; Sheiko S. S.; Matyjaszewski K.Stimuli-responsive molecular brushes. Prog. Polym. Sci., 2010, 35(1-2), 24-44. doi:10.1016/j.progpolymsci.2009.11.002http://dx.doi.org/10.1016/j.progpolymsci.2009.11.002
Liu Y. J.; Wang J. L.; Zhang M. Y.; Li H. M.; Lin Z. Q.Polymer-ligated nanocrystals enabled by nonlinear block copolymer nanoreactors: synthesis, properties, and applications. ACS Nano, 2020, 14(10), 12491-12521. doi:10.1021/acsnano.0c06936http://dx.doi.org/10.1021/acsnano.0c06936
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