Dynamic Bonds between Boronic Acid and Alginate: Hydrogels with Stretchable, Self-Healing, Stimuli-Responsive, Remoldable, and Adhesive Properties

Hong, Sang Hyeon; Kim, Sun‐Jin; Park, Joseph P.; Shin, Mikyung; Kim, Keumyeon; Ryu, Gi-Hyung; Lee, Haeshin

doi:10.1021/acs.biomac.8b00144

Cited by 157 publications

(131 citation statements)

References 40 publications

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“…Due to catalyst‐free rapid dynamic exchange at ambient conditions and in aqueous media, this reaction has been utilized in stimuli‐responsive hydrogels with dynamic properties . Sumerlin et al.…”

Section: Boronic Esters and Boronatesmentioning

confidence: 99%

Dynamic Covalent Bonds in Polymeric Materials

2019

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Dynamic covalent bonds (DCBs) have received significant attention over the past decade. These are covalent bonds that are capable of exchanging or switching between several molecules. Particular focus has recently been on utilizing these DCBs in polymeric materials. Introduction of DCBs into a polymer material provides it with powerful properties including self‐healing, shape‐memory properties, increased toughness, and ability to relax stresses as well as to change from one macromolecular architecture to another. This Minireview summarizes commonly used powerful DCBs formed by simple, often “click” reactions, and highlights the powerful materials that can result. Challenges and potential future developments are also discussed.

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Section: Boronic Esters and Boronatesmentioning

confidence: 99%

Dynamic Covalent Bonds in Polymeric Materials

2019

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“…Even so, intrinsic healing materials, capable of healing under ambient conditions are generally soft and deformable and mostly in the form of hydrogels or elastomers that feature high polymer chain mobility/flexibility. 6,23,25,[33][34][35][36][37][38][39][40][41][42] Unfortunately, it is a formidable challenge to fabricate high-strength and stiff polymeric materials that could heal damages intrinsically under ambient conditions. This is because the diffusion of the polymer chains in rigid materials is hindered significantly, and the rigidity is not favorable for the intimate contact between fractured interfaces.…”

Section: Introductionmentioning

confidence: 99%

Mechanically Strong and Highly Stiff Supramolecular Polymer Composites Repairable at Ambient Conditions

Zhu

Chen

et al. 2020

CCS Chem

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It is a formidable challenge to fabricate healable polymeric materials with high mechanical strength and stiffness due to the highly suppressed diffusion of their polymer chains. Herein, a high-strength, highly stiff, and repairable/healable supramolecular polymer composite was fabricated by complexing poly(acrylic acid) (PAA) and poly(allylamine hydrochloride) (PAH) in aqueous solutions, followed by molding into desired shapes. Exquisitely tuning the electrostatic and H-bonding interactions between PAA and PAH led to associative phase-separation and in situ formation of nanostructures in the resultant PAA-PAH composites. The H-bonded assembly of PAA-PAH complexes existed as nanospheres were dispersed homogeneously in the continuous phase as an electrostatic assembly of PAA-PAH complexes. Such a structural feature endowed the PAA-PAH copolymer with a doublecross-linked structure, enabling significant reinforcement of the material. a The PAA-PAH composites exhibited a tensile strength and an elastic modulus as high as ∼ 67 MPa and ∼ 2.0 GPa, respectively. Due to the benefits from the reconstruction of the complexes, such as reversible electrostatic interactions and H-bonds between PAA and PAH, the PAA-PAH composite could be repaired/healed readily under ambient conditions (25°C, 40% humidity) by using the liquid-like form of the PAA-PAH complexes (i.e., coacervate). The healing strategy reported here provides a supplementary method for easy repair or healing of high-strength and stiff supramolecular polymer materials.

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“…Polymer networks that contain dynamic reversible bonds exhibit unusual properties such as extraordinary toughness, self‐healing capabilities, and time dependent reversible elasticity . These networks typically use reversible interactions such as metal–ligand coordination bonds, hydrogen bonds, ionic bonds, and hydrophobic interactions . Catechol motifs are of particular interest owing to their ability to form many types of reversible bonds .…”

Section: Methodsmentioning

confidence: 99%

Dynamic Contributions to the Bulk Mechanical Properties of Self‐Assembled Polymer Networks with Reconfigurable Bonds

Tang

Wang

Eristoff

et al. 2019

Macromol. Rapid Commun.

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Catechol motifs are of particular interest owing to their ability to form many types of reversible bonds. [15][16][17][18][19] Polymer networks with catechol-cation coordination bonds have relaxation times that are governed by the affinity of the cation with the catechol group. [20][21][22] Grindy et al. [23] measured the viscoelastic modulus for networks with kinetically distinct metal coordinate crosslinks and demonstrated that reversible coordination junctions dominate the viscoelasticity of bulk materials. Catechol motifs with two hydroxy groups can also form hydrogen bonds among themselves. [24] Comparatively, there have been few reports on the role of hydrogen bonds between catechols in crosslinked networks. [25] Furthermore, the role of catechol concentration on bulk mechanics of polymer networks has yet to be elucidated in networks composed of model polymers. Here, we describe the role of hydrogen-bonded catechols on the bulk mechanical properties of the resulting networks.We recently synthesized catecholbearing ABA triblock copolymers that can self-assemble into mechanically robust networks wherein physical crosslinks are stabilized by inter-chain hydrogen bonding. [26] The copoly mer is synthesized through three steps and is processed into a network as shown in Scheme 1. Poly(ethylene glycol)-bromide (PEG-Br) macroinitiators are first prepared and then extended with an active esterified methacrylic acid (N-hydroxysuccinimide ester; NHSMA) by atom transfer radical polymerization. A blocks are then conjugated with dopamine to produce poly(NHSMA) 60 -b-PEG 227 -b-poly(NHSMA) 60 -Cat (ABA-Cat) polymers with a targeted conjugation ratio (r cat ) defined as the fraction of NHSMA monomers functionalized with a pendant catechol. Solutions of ABA-Cat polymer in N,Ndimethylformamide (DMF) self-assemble into networks through solvent exchange with water. We posit the network contains physical crosslinks composed of catechol-rich A blocks bridged together by PEG-based B blocks for following reasons. First, A and B blocks are immiscible in water and will be phase separated. Our previous study on structure showed solvent exchange disrupts crystalized PEG block by differential scanning calorimetry [26] and hydrogen-bonded Soft materials that contain dynamic and reversible bonds exhibit unique properties including unusual extensibility, reversible elasticity, and self-healing capabilities, for example. Catechol motifs are of particular interest owing to their ability to form many kinds of reversible bonds; however, there are few reports on the role of hydrogen bonds between catechols. Here, physically crosslinked self-assembled networks composed of catechol-functionalized ABA triblock co-polymers are synthesized and characterized to elucidate the role of intermolecular bonding between catechol motifs on bulk mechanical properties. The Young's moduli of equilibrated networks range from 16 to 43 MPa. Furthermore, the concentration of intermolecular interaction is controlled indirectly by synthesizing polymers with prescri...

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Dynamic Bonds between Boronic Acid and Alginate: Hydrogels with Stretchable, Self-Healing, Stimuli-Responsive, Remoldable, and Adhesive Properties

Cited by 157 publications

References 40 publications

Dynamic Covalent Bonds in Polymeric Materials

Dynamic Covalent Bonds in Polymeric Materials

Mechanically Strong and Highly Stiff Supramolecular Polymer Composites Repairable at Ambient Conditions

Dynamic Contributions to the Bulk Mechanical Properties of Self‐Assembled Polymer Networks with Reconfigurable Bonds

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