2022 |
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Kim, Ki Hyun; Nam, Jiyun; Choi, Jinwoong; Seo, Myungeun; Bang, Joona From macromonomers to bottlebrush copolymers with sequence control: synthesis, properties, and applications Journal Article Polym. Chem., 13 (16), pp. 2224-2261, 2022, ISBN: 1759-9954. Abstract | BibTeX | Tags: Block polymer Bottlebrush polymer Polymer synthesis @article{Bang2022, title = {From macromonomers to bottlebrush copolymers with sequence control: synthesis, properties, and applications}, author = {Ki Hyun Kim AND Jiyun Nam AND Jinwoong Choi AND Myungeun Seo AND Joona Bang}, url = {https://pubs.rsc.org/en/content/articlelanding/2022/py/d2py00126h}, doi = {10.1039/D2PY00126H }, isbn = {1759-9954}, year = {2022}, date = {2022-03-14}, journal = {Polym. Chem.}, volume = {13}, number = {16}, pages = {2224-2261}, abstract = {Bottlebrush polymers (BBPs) are a type of comb-like macromolecule with densely grafted polymeric sidechains attached to the polymer backbones, and many intriguing properties and applications have been demonstrated due to their unique architecture. Moreover, a ring-opening metathesis polymerization (ROMP) technique using Grubbs catalysts allows a precise control of various structural parameters in BBPs, such as the sidechain length, backbone length, and sidechain microstructures. This review mainly highlights recent advances of BBPs prepared by ROMP, from synthesis efforts to properties and applications.}, keywords = {Block polymer, Bottlebrush polymer, Polymer synthesis}, pubstate = {published}, tppubtype = {article} } Bottlebrush polymers (BBPs) are a type of comb-like macromolecule with densely grafted polymeric sidechains attached to the polymer backbones, and many intriguing properties and applications have been demonstrated due to their unique architecture. Moreover, a ring-opening metathesis polymerization (ROMP) technique using Grubbs catalysts allows a precise control of various structural parameters in BBPs, such as the sidechain length, backbone length, and sidechain microstructures. This review mainly highlights recent advances of BBPs prepared by ROMP, from synthesis efforts to properties and applications. | |
2021 |
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Nam, Jiyun; Kwon, Sangwoo; Yu, Yong-Guen; Seo, Ho-Bin; Lee, Jae-Suk; Lee, Won Bo; Kim, YongJoo; Seo, Myungeun Folding of sequence-controlled graft copolymers to subdomain-defined single-chain nanoparticles Journal Article Macromolecules, 54 (18), pp. 8829-8838, 2021, ISBN: 0024-9297. Abstract | BibTeX | Tags: CCS polymer Cross-linking Graft copolymer Polymer particle Polymer synthesis ROMP Self-assembly @article{Seo2021b, title = {Folding of sequence-controlled graft copolymers to subdomain-defined single-chain nanoparticles}, author = {Jiyun Nam AND Sangwoo Kwon AND Yong-Guen Yu AND Ho-Bin Seo AND Jae-Suk Lee AND Won Bo Lee AND YongJoo Kim AND Myungeun Seo}, url = {https://pubs.acs.org/doi/full/10.1021/acs.macromol.1c01674}, doi = {10.1021/acs.macromol.1c01674}, isbn = {0024-9297}, year = {2021}, date = {2021-09-17}, journal = {Macromolecules}, volume = {54}, number = {18}, pages = {8829-8838}, abstract = {We developed a methodology, inspired by the folding of proteins, for the precision synthesis of hairy polymer nanoparticles. High-molar mass and narrowly dispersed graft copolymers were synthesized by graft-through ring opening metathesis polymerization, to incorporate a designated number of side chains and dimerizable cinnamic acid groups. Intrachain photodimerization collapsed the backbone and arrested it into a compact globular conformation, resulting in hairy nanoparticles topologically equivalent to a core cross-linked star polymer. The single-chain collapse process translates the molecular information written on the 1D graft copolymer into the 3D globular polymer nanoparticle, like protein folding. Unprecedented control over structural parameters was achieved, including the length, number, and composition of the side chains as well as cross-linking density. Different side chains formed distinct subdomains in the sterically congested nanoparticle state and further self-assembled into micellar aggregates in a selective solvent. Both experimental observations and computational simulations indicated that preorganization of the side chains in the block sequence produces subdomains which primarily follow the backbone length scale, while random sequences showed side chain-dependent scaling. Polymer nanoparticles with discrete multiple subdomains were produced by folding of the ternary block graft copolymers. Drastic differences in the self-assembly behavior of ABC- and ACB-sequenced nanoparticles indicate that the spatial organization of subdomains can be achieved by sequence control.}, keywords = {CCS polymer, Cross-linking, Graft copolymer, Polymer particle, Polymer synthesis, ROMP, Self-assembly}, pubstate = {published}, tppubtype = {article} } We developed a methodology, inspired by the folding of proteins, for the precision synthesis of hairy polymer nanoparticles. High-molar mass and narrowly dispersed graft copolymers were synthesized by graft-through ring opening metathesis polymerization, to incorporate a designated number of side chains and dimerizable cinnamic acid groups. Intrachain photodimerization collapsed the backbone and arrested it into a compact globular conformation, resulting in hairy nanoparticles topologically equivalent to a core cross-linked star polymer. The single-chain collapse process translates the molecular information written on the 1D graft copolymer into the 3D globular polymer nanoparticle, like protein folding. Unprecedented control over structural parameters was achieved, including the length, number, and composition of the side chains as well as cross-linking density. Different side chains formed distinct subdomains in the sterically congested nanoparticle state and further self-assembled into micellar aggregates in a selective solvent. Both experimental observations and computational simulations indicated that preorganization of the side chains in the block sequence produces subdomains which primarily follow the backbone length scale, while random sequences showed side chain-dependent scaling. Polymer nanoparticles with discrete multiple subdomains were produced by folding of the ternary block graft copolymers. Drastic differences in the self-assembly behavior of ABC- and ACB-sequenced nanoparticles indicate that the spatial organization of subdomains can be achieved by sequence control. |