A Programmed Polymer Folding: Click and Clip Construction of Doubly Fused Tricyclic and Triply Fused Tetracyclic Polymer Topologies

Sugai, Naoto; Heguri, Hiroyuki; Yamamoto, Takuya; Tezuka, Yasuyuki

doi:10.1021/ja209394m

Cited by 70 publications

(71 citation statements)

References 27 publications

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“…[8][9][10][11][12][13][14] Although the design and synthesis of single chain objects has recently received great attention, 15 the development in this field is still in its initial phase. So far, several types of strategies to mediate the single chain collapse to form SCNPs have been explored, [16][17][18][19][20][21][22] ranging from hydrogen bonding, 23-27, 10, 28-31 covalent bonding, [32][33][34][35][36] to dynamic covalent bonding. [37][38][39][40] All these recent advances have provided versatile approaches to induce the folding of a single polymer chain.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Sequence-Controlled Multiblock Single Chain Nanoparticles by a Stepwise Folding–Chain Extension–Folding Process

et al. 2016

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Copyright and reuse:The Warwick Research Archive Portal (WRAP) makes this work by researchers of the University of Warwick available open access under the following conditions. Copyright © and all moral rights to the version of the paper presented here belong to the individual author(s) and/or other copyright owners. To the extent reasonable and practicable the material made available in WRAP has been checked for eligibility before being made available.Copies of full items can be used for personal research or study, educational, or not-for profit purposes without prior permission or charge. Provided that the authors, title and full bibliographic details are credited, a hyperlink and/or URL is given for the original metadata page and the content is not changed in any way. Publisher's statement:"This document is the Accepted Manuscript version of a Published Work that appeared in final form in Macromolecules copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work http://pubs.acs.org/page/policy/articlesonrequest/index.html ." A note on versions:The version presented here may differ from the published version or, version of record, if you wish to cite this item you are advised to consult the publisher's version. Please see the 'permanent WRAP URL above for details on accessing the published version and note that access may require a subscription. ABSTRACTThe specific activity of proteins can be traced back to their highly defined tertiary structure, which is a result of a perfectly controlled intra-chain folding process. In the herein presented work the folding of different distinct domains within a single macromolecule is demonstrated. RAFT polymerization was used to produce multi-block copolymers, which are decorated with pendant hydroxyl groups in foldable sections, separated by non-functional spacer blocks in between. OH-bearing blocks were folded using an isocyanate cross linker prior to chain extension to form single chain nanoparticles (SCNP). After addition of a spacer block and a further OH decorated block, folding was repeated to generate individual SCNP within a polymer chain. Control experiments were performed indicating the absence of inter block cross linking. SCNP were found to be condensed by a combination of covalent and supra molecular (hydrogen bonds) linkage. The approach was used to create a highly complex penta-block copolymer having three individually folded subdomains with an overall dispersity of 1.21. The successful formation of SCNP was confirmed by size exclusion chromatography (SEC), nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC) and atomic force microscopy (AFM).

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Section: Introductionmentioning

confidence: 99%

Synthesis of Sequence-Controlled Multiblock Single Chain Nanoparticles by a Stepwise Folding–Chain Extension–Folding Process

et al. 2016

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“…These values are in good agreement with <G exp > values reported in the literature for 8-shaped PS. [18] However, no dependence can be found between <G exp > and the variation of polymer molecular weights. These results indicate that the observed fluctuations of <G exp > for PS and PDMA may be ascribed to the difference of the polymer architectures.…”

Section: Cyclization Reactionmentioning

confidence: 99%

“…[1] Cyclic topological polymers, including single and multiple cyclic polymers, due to the absence of end groups, exhibit unique properties as compared to their linear and branched counterparts. Among these cyclic structures, bicyclic polymers, such as theta-shaped, [2][3][4][5][6][7] 8-shaped, [7,[8][9][10][11][12][13][14][15][16][17] and manacle-shaped constructions, [6,7,18,19] are an important class of cyclic topological polymers. Although the 8-shaped polymer has been investigated the most, efficient and practical synthesis of this polymer architecture still remains challenge.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of well-defined 8-shaped polymers by the combination of RAFT polymerization and click reaction

Wang

Yang

et al. 2013

Designed Monomers and Polymers

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A series of well-defined 8-shaped polymers have been synthesized by the combination of reversible addition-fragmentation chain transfer (RAFT) polymerization and click reaction. Firstly, well-defined, azide-terminated, four-armed star polymers including poly(N,N-dimethylacrylamide) and polystyrene were prepared by RAFT polymerization using pentaerythritoltetrakis(3-(S-(2-azidoethylcarbonoyl)trithiocarbonyl)propanoate) as a chain transfer agent. Then, intramolecular cyclization of the azide-functionalized four-armed precursors was conducted under highly dilution conditions using a bifunctional N,N-bis(2-propargyloxycarbonyl ethyl)-2-hydroxylethyl amine as the linker, affording 8-shaped polymers. FTIR, 1 H NMR, GPC, and MLADI-TOF MS analysis confirmed that the coupling reaction proceeded via the cyclization manner.

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“…57 The ESA-CF process, in conjunction with a tandem alkyne-azide click and an olefin metathesis clip reaction, has now been developed as an effective means for the production of programmed folding forms by synthetic polymers, such as a doubly fused tricyclic g-graph and a triply fused tetracyclic unfolded tetrahedron graph construction (Scheme 12). 58 A summary of the synthetic procedure and characterization of the g-graph polymer is described as a typical example. 58 Thus, a cyclic poly(THF) precursor with an allyloxy and alkyne group was first synthesized by the ESA-CF protocol.…”

Section: Fused-multicyclic Constructionsmentioning

confidence: 99%

“…58 A summary of the synthetic procedure and characterization of the g-graph polymer is described as a typical example. 58 Thus, a cyclic poly(THF) precursor with an allyloxy and alkyne group was first synthesized by the ESA-CF protocol. A linear poly(THF) with azide end groups was prepared by simply terminating a living polymerization of THF with tetrabutylammonium azide.…”

Section: Fused-multicyclic Constructionsmentioning

confidence: 99%

Topological polymer chemistry for designing multicyclic macromolecular architectures

Tezuka

2012

Polym J

Self Cite

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The geometrical conception and current synthetic challenges of topological polymer chemistry have been reviewed. On the basis of the systematic classification and isomeric properties of polymer chain topologies, a variety of novel multicyclic macromolecular constructions have now been rationally designed and subsequently realized by intriguing synthetic protocols. In particular, cyclic and multicyclic polymer products are effectively produced by an electrostatic polymer self-assembly of telechelic precursors that contain cyclic ammonium salt groups accompanying polyfunctional carboxylate counteranions and the subsequent covalent conversion through the ring-opening or through the ring-emitting reaction of the cyclic ammonium salt groups by carboxylate counteranions (Electrostatic Self-assembly and Covalent Fixation (ESA-CF) process). Furthermore, the ESA-CF process, in conjunction with effective linking/cleaving chemistry (including the metathesis condensation (clip) and alkyne-azide addition (click) reactions), has been demonstrated as a new synthetic protocol for unprecedented multicyclic macromolecular topologies.

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A Programmed Polymer Folding: Click and Clip Construction of Doubly Fused Tricyclic and Triply Fused Tetracyclic Polymer Topologies

Cited by 70 publications

References 27 publications

Synthesis of Sequence-Controlled Multiblock Single Chain Nanoparticles by a Stepwise Folding–Chain Extension–Folding Process

Synthesis of Sequence-Controlled Multiblock Single Chain Nanoparticles by a Stepwise Folding–Chain Extension–Folding Process

Synthesis of well-defined 8-shaped polymers by the combination of RAFT polymerization and click reaction

Topological polymer chemistry for designing multicyclic macromolecular architectures

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