One-pot synthesis of block-copolyrotaxanes through controlled <i>rotaxa</i>-polymerization

Hilschmann, Jessica; Wenz, Gerhard; Kali, Gergely

doi:10.3762/bjoc.13.127

Cited by 7 publications

(10 citation statements)

References 39 publications

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“…In this report, we have attempted to prepare topological gels in a single-step fashion using simultaneous free radical polymerization of isoprene and vinyl modified β-CyD (V-β-CyD) (Scheme 1). We expected that the obtained copolymer would append β-CyD moieties, and that the appended β-CyD can include another copolymer chain because the polyisoprene component acts as a guest for β-CyD [9][10][11][12]. In the expected structure ( Fig.…”

Section: Introductionmentioning

confidence: 98%

“…In the obtained polyrotaxane, the isoprene components of the copolymer were covered with methylated β-CyD, and the styrene components of the copolymer acted as a stopper to avoid dethreading of the methylated β-CyD. They have described this type of polymerization as rotaxa-polymerization [9][10][11]. Additionally, they demonstrated the applicability of many kinds of vinyl monomers and CyD derivatives in rotaxa-polymerization and showed a broad lineup of polyrotaxanes.…”

Section: Introductionmentioning

confidence: 99%

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Single-step preparation of topological gels using vinyl-modified β-cyclodextrin as a figure-of-six cross-linker

Kobayashi

Kojima

Miki

et al. 2018

J Incl Phenom Macrocycl Chem

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Herein, we have proposed a single-step preparation of topological gels using vinyl-modified βcyclodextrin (V-β-CyD) and isoprene. Copolymerization of V-β-CyD and isoprene in an aqueous solution resulted in gelation due to V-β-CyD acting as a novel type of copolymer chain cross-linker. The vinyl moiety of V-β-CyD becomes a part of the copolymer, while the β-CyD moiety of V-β-CyD simultaneously incorporates the isoprene component of the copolymer. V-β-CyD is capable of two different modes of cross-linking at each end, i.e., chemically bonding and mechanically interlocking. Due to the shape of the cross-linking point, we refer to it as figure-of-six cross-linking. Nuclear magnetic resonance (NMR) analysis showed that the gel contained V-β-CyD and isoprene in an approximately 1:0.3 stoichiometry. The relatively high content of β-CyD was reflected in the character of the gel; the gel swelled in dimethylformamide (DMF) which is a good solvent of β-CyD. A fluorometric analysis using 6-(p-toluidino)-2-naphthalenesulfonic acid (TNS) showed that the appended β-CyD was able to accommodate guest molecules. Introduction of an additional vinyl monomer into the gel was also successful. Addition of 4-vinylphenylboronic acid to the preparation procedure yielded a sugar-responsive gel that swelled in the presence of D-fructose.

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Section: Introductionmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

Single-step preparation of topological gels using vinyl-modified β-cyclodextrin as a figure-of-six cross-linker

Kobayashi

Kojima

Miki

et al. 2018

J Incl Phenom Macrocycl Chem

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“…Nowadays, topological gels have appeared as the third type of gels. They have attracted much attentions because of their special features originated from topological structures in which polymers are cross-linked by mechanically interlocked structures [1][2][3][4][5][6][7][8][9][10].…”

Section: Introductionmentioning

confidence: 99%

“…RPG was named after the concept of rotaxa-polymerization demonstrated by the Wenz group [6][7][8]. Their most important finding is that polymerization and rotaxanation can occur simultaneously.…”

Section: Introductionmentioning

confidence: 99%

Rotaxa-polymeric-gelation of acrylamides with vinyl-β-cyclodextrin

Kobayashi

Kojima

Miki

et al. 2020

J Incl Phenom Macrocycl Chem

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Previously, we have reported a single-step preparation method for a topological gel by copolymerizing isoprene and vinyl-modified β-cyclodextrin (V-β-CyD). In the prepared gel, the vinyl part of V-β-CyD consists a part of the copolymer chain, and the β-CyD part includes another copolymer chain, thus Vβ-CyD works as a cross-linker. We call the procedure rotaxa-polymeric-gelation (RPG) because polymerization, rotaxane formation, and gelation proceed simultaneously. In this study, we applied acrylamide (AAm) instead of isoprene for RPG, and successfully obtained highly swellable hydrogel.By contrast, a combination of V-β-CyD and N-isopropylacrylamide (NIPAAm) was not suitable for RPG because NIPAAm and cavity of β-CyD were mismatched in size. In addition, we prepared threecomponent gels. Among of them, gels composed of NIPAAm, isoprene, and V-β-CyD showed thermoresponsiveness by reflecting the character of polyNIPAAm. These results provide an insight for usage of vinyl monomers for RPG strategy.

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“…The concurrent radical copolymerization of 1,3-dienes and bulky stoppers in the presence of CDs (so-called rotaxa -polymerization) was further applied for the syntheses of water-soluble polyisoprene polyrotaxanes [ 25 ]. Furthermore, ABA-type block-copolyrotaxanes could be synthesized using this polymerization technique controlled by RAFT chain transfer agents [ 26 ].…”

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confidence: 99%