Intrinsic self-healing polymeric materials are substances that relieve external stress and restore their original mechanical properties after extreme damage via dynamic covalent bonding in the polymeric structure or the reversible association of supramolecular motifs. Boronic ester-based dynamic covalent bonds formed between boronic acids and diols impart excellent self-healing properties to the hydrogels, organic gels, elastomers, and plastics depending on the characteristics of the corresponding polymer. In addition, these bonds induce internal reorganization in the chemical/physical structure in response to changes in the biological signals and biomaterials, such as hydrophilicity, pH, and the presence of glucose. This multi-responsiveness to stimuli as well as the self-healing, injectability, and biocompatibility of boronic ester-based polymers have led to several technological achievements with applicability in biomedical fields, including drug delivery, medical adhesion, bioimplants, and healthcare monitoring. This review provides an overview of various self-healing polymeric materials based on reversible B–O bonds, with a focus on boronic/boronate esters, borax, and benzoxaborole and their properties, responses to external stimuli, and applications.

Self-repairable materials strive to emulate curable and resilient biological tissue; however, their performance is currently insufficient for commercialization purposes because mending and toughening are mutually exclusive. Herein, we report a carbonate-type thermoplastic polyurethane elastomer that self-heals at 35 °C and exhibits a tensile strength of 43 MPa; this elastomer is as strong as the soles used in footwear. Distinctively, it has abundant carbonyl groups in soft-segments and is fully amorphous with negligible phase separation due to poor hard-segment stacking. It operates in dual mechano-responsive mode through a reversible disorder-to-order transition of its hydrogen-bonding array; it heals when static and toughens when dynamic. In static mode, non-crystalline hard segments promote the dynamic exchange of disordered carbonyl hydrogen-bonds for self-healing. The amorphous phase forms stiff crystals when stretched through a transition that orders inter-chain hydrogen bonding. The phase and strain fully return to the pre-stressed state after release to repeat the healing process.

Aluminum-coated polypropylene films are commonly used in food packaging because aluminum is a great gas barrier. However, recycling these films is not economically feasible. In addition, their end-of-life incineration generates harmful alumina-based particulate matter. In this study, coating layers with excellent gas-barrier properties are assembled on polypropylene films through layer-by-layer (LbL) deposition of biorenewable nanocellulose and nanochitin. The coating layers significantly reduce the transmission of oxygen and water vapors, two unfavorable gases for food packaging, through polypropylene films. The oxygen transmission rate of a 60 μm-thick, 20 LbL-coated polypropylene film decreases by approximately a hundredfold, from 1118 to 13.10 cc m^-2 day^-1 owing to the high crystallinity of nanocellulose and nanochitin. Its water vapor transmission rate slightly reduces from 2.43 to 2.13 g m^-2 day^-1. Furthermore, the coated film is highly transparent, unfavorable to bacterial adhesion and thermally recyclable, thus promising for advanced food packaging applications.

The demand for face masks is increasing exponentially due to the coronavirus pandemic and issues associated with airborne particulate matter (PM). However, both conventional electrostatic‐ and nanosieve‐based mask filters are single‐use and are not degradable or recyclable, which creates serious waste problems. In addition, the former loses function under humid conditions, while the latter operates with a significant air‐pressure drop and suffers from relatively fast pore blockage. Herein, a biodegradable, moisture‐resistant, highly breathable, and high‐performance fibrous mask filter is developed. Briefly, two biodegradable microfiber and nanofiber mats are integrated into a Janus membrane filter and then coated by cationically charged chitosan nanowhiskers. This filter is as efficient as the commercial N95 filter and removes 98.3% of 2.5 µm PM. The nanofiber physically sieves fine PM and the microfiber provides a low pressure differential of 59 Pa, which is comfortable for human breathing. In contrast to the dramatic performance decline of the commercial N95 filter when exposed to moisture, this filter exhibits negligible performance loss and is therefore multi‐usable because the permanent dipoles of the chitosan adsorb ultrafine PM (e.g., nitrogen and sulfur oxides). Importantly, this filter completely decomposes within 4 weeks in composting soil.