Versatile synthesis of end-reactive polyrotaxanes applicable to fabrication of supramolecular biomaterials

Tamura, Atsushi; Arisaka, Yoshinori; Yui, Nobuhiko

doi:10.3762/bjoc.12.287

Cited by 8 publications

(9 citation statements)

References 38 publications

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“…Polyrotaxanes (PRXs) are supermolecules composed of a linear polymer such as poly(ethylene glycol) (PEG) that is threaded into cyclic molecules such as α-cyclodextrins (α-CDs) and capped with bulky molecules (Figure 1a) [15,16]. Since there is no covalent bond between the polymer axle and the cyclic molecules, the threading cyclic molecules in PRXs can freely rotate or move along the polymer axle [17,18]. Owing to their intramolecular mobility property, PRXs have diverse biomedical application potential, such as in regulating cell adhesion and differentiation and for enhancing cell internalization [19,20,21].…”

Section: Introductionmentioning

confidence: 99%

Mechanically Reinforced Gelatin Hydrogels by Introducing Slidable Supramolecular Cross-Linkers

et al. 2019

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Tough mechanical properties are generally required for tissue substitutes used in regeneration of damaged tissue, as these substitutes must be able to withstand the external physical force caused by stretching. Gelatin, a biopolymer derived from collagen, is a biocompatible and cell adhesive material, and is thus widely utilized as a component of biomaterials. However, the application of gelatin hydrogels as a tissue substitute is limited owing to their insufficient mechanical properties. Chemical cross-linking is a promising method to improve the mechanical properties of hydrogels. We examined the potential of the chemical cross-linking of gelatin hydrogels with carboxy-group-modified polyrotaxanes (PRXs), a supramolecular polymer comprising a poly(ethylene glycol) chain threaded into the cavity of α-cyclodextrins (α-CDs), to improve mechanical properties such as stretchability and toughness. Cross-linking gelatin hydrogels with threading α-CDs in PRXs could allow for freely mobile cross-linking points to potentially improve the mechanical properties. Indeed, the stretchability and toughness of gelatin hydrogels cross-linked with PRXs were slightly higher than those of the hydrogels with the conventional chemical cross-linkers 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC)/N-hydroxysuccinimide (NHS). In addition, the hysteresis loss of gelatin hydrogels cross-linked with PRXs after repeated stretching and relaxation cycles in a hydrated state was remarkably improved in comparison with that of conventional cross-linked hydrogels. It is considered that the freely mobile cross-linking points of gelatin hydrogels cross-linked with PRXs attenuates the stress concentration. Accordingly, gelatin hydrogels cross-linked with PRXs would provide excellent mechanical properties as biocompatible tissue substitutes exposed to a continuous external physical force.

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Section: Introductionmentioning

confidence: 99%

Mechanically Reinforced Gelatin Hydrogels by Introducing Slidable Supramolecular Cross-Linkers

et al. 2019

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“…However, the size of 4‐vinylbenzoic acid may be insufficient to serve as a capping agent for a typical pseudo‐polyrotaxane composed of PEG and α‐CDs. Previously, we reported a synthesis method for polyrotaxanes using PEGs with terminally molecular hooks of 2‐amino‐3‐phenylpropyl groups (PEG‐Phe‐NH 2 ) as an axis polymer and 4‐substituted benzoic acid as a capping agent 26,28 . The combination of the molecular hooks and 4‐substituted benzoic acid can increase the bulkiness of the terminals, thereby succeeding in preventing the de‐threading of α‐CDs from the axis polymer.…”

Section: Resultsmentioning

confidence: 99%

“…Polyrotaxanes capped with 4‐vinylbenzoic acid (PRX‐VBn) were prepared by a minor modification of our method available in literature (Figure 2). 26 PEG‐OH (20.0 g, 4.3 mmol), TEA (9.3 ml, 66.4 mmol), and MsCl (3.4 ml, 44.4 mmol) were allowed to react in anhydrous THF (115 ml) for 5 h at 23°C. The filtrate of the reaction solution was added dropwise to diethyl ether to reprecipitate the polymer.…”

Section: Methodsmentioning

confidence: 99%

Terminally cross‐linking polyrotaxane hydrogels applicable for cellular microenvironments

Arisaka

Tamura

Yui

2020

J of Applied Polymer Sci

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Polyrotaxanes, composed of multiple cyclic molecules threaded onto a polymer chain axis capped with bulky molecules, exhibit unique structural features wherein cyclic molecules can move along a chain. We have previously constructed biointerfaces that utilize the molecular mobility of polyrotaxanes for controlling cellular responses. To implement the features in a threedimensionally engineered cellular microenvironment, this study developed supramolecular hydrogels using polyrotaxane cross-linkers capped with 4-vinylbenzyl groups at the terminals of a polymer chain axis, where the 4-vinylbenzyl groups in the polyrotaxane allow polymerization with other polyrotaxanes to form polyrotaxane networks. Polyrotaxane hydrogels are successfully prepared without any additional monomers via redox polymerization. The dynamic viscoelasticity and swellability of the hydrogels can be varied depending on the concentration of the polyrotaxanes. When fibroblasts are cultured on hydrogels, sufficient adhesion for cultivation is observed. Therefore, polyrotaxane hydrogels demonstrate suitable potential as new supramolecular biomaterials with dynamic structural features.

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“…PRX-VBns were prepared according to our previously described method [ 34 ], with a minor modification ( Figure S2 in Supporting Information ). The typical procedure for synthesis of methylated PRX-VBns (Me 322 PRX-VBn in Table 1 ) is as follows: briefly, PRX-VBn (1.0 g, 36 µmol) was dissolved in dehydrated DMSO (81 mL).…”

Section: Methodsmentioning

confidence: 99%

Tissue Adhesion-Anisotropic Polyrotaxane Hydrogels Bilayered with Collagen

Hakariya

Arisaka

Masuda

et al. 2021

Gels

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Hydrogels are promising materials in tissue engineering scaffolds for healing and regenerating damaged biological tissues. Previously, we developed supramolecular hydrogels using polyrotaxane (PRX), consisting of multiple cyclic molecules threaded by an axis polymer for modulating cellular responses. However, since hydrogels generally have a large amount of water, their adhesion to tissues is extremely weak. Herein, we designed a bilayered hydrogel with a PRX layer and a collagen layer (PRX/collagen hydrogel) to achieve rapid and strong adhesion to the target tissue. The PRX/collagen hydrogel was fabricated by polymerizing PRX crosslinkers in water with placement of a collagen sponge. The differences in components between the PRX and collagen layers were analyzed using Fourier transform infrared spectroscopy (FT-IR). After confirming that the fibroblasts adhered to both layers of the PRX/collagen hydrogels, the hydrogels were implanted subcutaneously in mice. The PRX hydrogel without collagen moved out of its placement site 24 h after implantation, whereas the bilayer hydrogel was perfectly adherent at the site. Together, these findings indicate that the bilayer structure generated using PRX and collagen may be a rational design for performing anisotropic adhesion.

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Versatile synthesis of end-reactive polyrotaxanes applicable to fabrication of supramolecular biomaterials

Cited by 8 publications

References 38 publications

Mechanically Reinforced Gelatin Hydrogels by Introducing Slidable Supramolecular Cross-Linkers

Mechanically Reinforced Gelatin Hydrogels by Introducing Slidable Supramolecular Cross-Linkers

Terminally cross‐linking polyrotaxane hydrogels applicable for cellular microenvironments

Tissue Adhesion-Anisotropic Polyrotaxane Hydrogels Bilayered with Collagen

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