Boronic ester, one typical example of dynamic covalent bonds, has presented great potential to prepare selfhealing hydrogels. However, most of currently reported hydrogels based on boronic esters are formed at pH > 8, which impeded their further use in physiological conditions. In this study, we designed two kinds of zwitterionic copolymers with benzoxaborole and catechol pendant groups, respectively. Owing to the lower pK a value of benzoxaborole (7.2), gelation can happen easily at pH 7.4 PBS after mixing these two copolymers due to efficient formation of benzoxaborole-catechol complexations. The resulting hydrogels exhibited excellent self-healing property as well as dual pH/sugar responsiveness due to the dynamic nature of boronic ester. Moreover, benefiting from the cell membrane bioinspired 2-methacryloyloxyethyl phosphorylcholine (MPC)based polymeric matrix, the hydrogel was further investigated for 3D cell encapsulation. The combination of biocompatible zwitterionic polymers with dynamic benzoxaborole-catechol complexation makes the hydrogels a promising platform for diverse potential bioapplications like drug delivery and tissue engineering.

Injectable self-healing hydrogels, as implanted materials, have received great attention over the past decades. The tunable optical and mechanical properties as well as the ability to lower the risk of inflammatory responses are essential considerations for their applications in diverse bioengineering processes. In this work, we report a novel injectable selfhealing hydrogel with tunable optical, mechanical, and antimicrobial properties, fabricated by a multifunctional ABA triblock copolymer gelator, poly{(4 (methacryloyloxy)ethyl] trimethylammonium chloride]} and polyethylenimine. The self-healing capability of the hydrogel was demonstrated by rheology tests, and quantitative force measurements using a surface forces apparatus (SFA) provided molecular insights into the self-healing mechanism of Schiff base reaction. Additionally, the optical and mechanical properties of the hydrogel can be fine-tuned in a sensitive temperature-responsive manner because of the local nano-hydrophobic domains formed through the phase transition of the ABA triblock copolymer gelator. The hydrogel also demonstrated multiple sol−gel transitions subjected to pH change. Moreover, the hydrogel can also effectively inhibit the growth of both Gram-negative and Gram-positive bacteria (Escherichia coli and Staphylococcus aureus), while showing low cytotoxicity to both fibroblast and cancer cells (MRC-5 and HeLa). The novel multifunctional injectable self-healing hydrogel with tunable optical, mechanical, and excellent antimicrobial properties shows great potential in various bioengineering applications.

Conjugation of zwitterionic polymer with dopamine is a promising approach to endow the surface with antifouling properties for medical devices, biosensors and marine coating applications etc. Zwitterionic polymers can be conjugated with dopamine by mostly four methods.

Mussel-inspired dopamine chemistry has increasingly been used for surface modification due to its simplicity, versatility, and strong reactivity for secondary functionalization with amine or thiol containing molecules. In this work, we demonstrate a facile surface modification technique using dopamine chemistry to prepare a zwitterionic polymer coating with both antifouling and antimicrobial property. Catechol containing adhesive monomer dopamine methacrylamide (DMA) was copolymerized with bioinspired zwitterionic 2-methacryloyloxyethyl phosphorylcholine (MPC) monomer, and the synthesized copolymers were covalently grafted onto the amino (−NH 2 ) rich polyethylenimine (PEI)/polydopamine (PDA) codeposited surface to obtain a stable antifouling surface. The resulting surface was later used for in situ deposition of antimicrobial silver nanoparticles (AgNPs), facilitated by the presence of catechol groups of the coating. The modified surface was characterized using X-ray photoelectron spectroscopy (XPS), water contact angle measurements, and atomic force microscopy (AFM). This dual functional coating significantly reduced the adhesion of both Gram-negative Escherichia coli and Gram-positive Staphylococcus aureus bacteria and showed excellent resistance to bovine serum albumin (BSA) adsorption. This bioinspired and efficient surface modification strategy with dual functional coating promises its potential application in implantable biomedical devices.

Developing effective internal wound dressing materials is important for postoperative tissue regeneration while remains a challenge due to the poor biological environment-adaptability of conventional materials. Here, we report an example of injectable self-healing hydrogel based on gastric environment-adaptive supramolecular assembly, and have explored its application for gastric perforation healing. By leveraging the gastric environment-modulated supramolecular interactions, the self-assembled hydrogel network is orchestrated with sensitive thermo-responsibility, injectability, printability and rapid self-healing capability. The hydrogel dressing can effectively inhibit the attachment of microorganisms and demonstrates outstanding antibiofouling property. In vivo rat model further demonstrates the as-prepared hydrogel dressing simplifies the surgical procedures, reduces postoperative complications as well as enhances the healing process of gastric perforation compared with the conventional treatment. This work provides useful insights into the development of biological environment-adaptive functional materials for various biomedical applications.

The development and application of natural antibacterial materials have always been the focus of biomedical research. Borneol as a natural antibacterial compound has received extensive attention. However, the hydrophobicity caused by its unique structure limits its application range to a certain extent. In this study, we combine zwitterionic 2-methacryloyloxyethyl phosphorylcholine (MPC) with a complex bicyclic monoterpene structure borneol compound and prepare an excellent antifouling and antibacterial surface via the Schiff-base bond. The prepared coating has excellent hydrophilicity verified by the contact angle (CA), and its polymer layer is confirmed by X-ray photoelectron spectroscopy (XPS). The zwitterion MPC and borneol moieties in the copolymer play a coordinating role, relying on super hydration and the special stereochemical structure to prevent protein adsorption and inhibit bacterial adhesion, respectively, which are demonstrated by bovine serum albumin (BSA) adsorption and antibacterial activity test. Moreover, the water-soluble borneol derivative as the antibacterial surfaces we designed here was biocompatible toward MRC-5 (lung fibroblasts), as showed by in vitro cytotoxicity assays. Such results indicate the potential application of the as-prepared hydrophilic surfaces in the biomedical materials.

The rapid accumulation of dead bacteria or protein on a bactericidal surface can reduce the effectiveness of the modified surface and alter its biocidal activity by shielding the surface biocide functional groups, promoting microbial attachment and subsequent biofilm formation. Thus, the alteration of biocidal activity due to biofilm formation can cause serious trouble including severe infection or implant or medical device failure leading to death. Therefore, developing a smart self-cleaning surface is of great interest. Ideally, such a surface can not only kill the attached microbials but also release the dead cells and foulants from the surface under a particular incitement on demand. In this project, a sugar-responsive self-cleaning coating has been developed by forming covalent boronic ester bonds between catechol groups from polydopamine and a benzoxaborole pendant from zwitterionic and cationic polymers. To incorporate antifouling properties and enhance the biocompatibility of the coating, bioinspired zwitterionic compound 2-methacryloyloxyethyl phosphorylcholine (MPC) was chosen and benzoxaborole pendant containing zwitterionic polymer poly­(MPC-st-MAABO) (MAABO: 5-methacrylamido-1,2-benzoxaborole) was synthesized. Additionally to impart antibacterial properties to the surface, a quaternary ammonium containing cationic polymer poly­(2-(methacryloyloxy)­ethyl trimethylammonium (META)-st-MAABO)) was synthesized. These synthesized polymers were covalently grafted to a polydopamine (PDA) coated surface by forming a strong cyclic boronic ester complex with a catechol group of the PDA layer endowing the surface with bacteria contact-killing properties and capturing specific protein. After the addition of cis-diol containing competitive molecules, i.e., saccharides/sugars, this boronic ester complex with a catechol group of PDA was replaced and the attached polymer layer was cleaved from the surface, resulting in the release of both absorbed protein and live/killed bacteria electrostatically attached to the polymer layer. This dynamic self-cleaning surface can be a promising material for biomedical applications avoiding the gathering of dead cells and debris that are typically encountered on a traditional biocidal surface.

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