No abstract

Living tissues, such as muscle, autonomously grow and remodel themselves to adapt to their surrounding mechanical environment through metabolic processes. By contrast, typical synthetic materials cannot grow and reconstruct their structures once formed. We propose a strategy for developing “self-growing” polymeric materials that respond to repetitive mechanical stress through an effective mechanochemical transduction. Robust double-network hydrogels provided with a sustained monomer supply undergo self-growth, and the materials are substantially strengthened under repetitive loading through a structural destruction-reconstruction process. This strategy also endows the hydrogels with tailored functions at desired positions by mechanical stamping. This work may pave the way for the development of self-growing gel materials for applications such as soft robots and intelligent devices.

Recent progresses in developing tough hydrogels promise the great potential of this class of soft and wet materials as biomaterials, soft robotics, smart actuators and sensors. [1][2][3][4][5][6][7][8][9][10] Any practical application of these hydrogels as smart materials, however, requires a combination of mechanical properties including stiffness, strength, toughness, and self-healing. For instance, along with the high strength and toughness, a cartilage substitute material requires a high stiffness to bear the load, while a blood vessel substitute material requires flexibility.Self-healing not only merits the long term durability of the load-bearing materials, but also gives possibility to reconstruct the material with desired shape from its microgels. While many hydrogels possess some of these requirements, it is a challenge to develop hydrogels satisfying all of these criteria. [2,[11][12][13] In this work, we report a new class of physical hydrogels that possess these multiple functions. These hydrogels are obtained from concentrated solution of oppositely charged polyelectrolytes. After dialysis of their small counter ions, the oppositely charged polyelectrolytes form polyion complexes of a wide strength distribution, which give dynamic crosslinking of an extremely wide life time scale. The strong, long life time bonds serve as permanent cross-linking, imparting elasticity, whereas the weak, short life

A series of physical double-network hydrogels is synthesized based on an amphiphilic triblock copolymer. The gel, which contains strong hydrophobic domains and sacrificial dynamic bonds of hydrogen bonds, is stiff and tough, and even stiffens in concentrated saline solution. Furthermore, due to its supramolecular structure, the gel features improved self-healing and self-recovery abilities

Natural structural materials (such as tendons and ligaments) are comprised of multiscale hierarchical architectures, with dimensions ranging from nano- to macroscale, which are difficult to mimic synthetically. Here a bioinspired, facile method to fabricate anisotropic hydrogels with perfectly aligned multiscale hierarchical fibrous structures similar to those of tendons and ligaments is reported. The method includes drying a diluted physical hydrogel in air by confining its length direction. During this process, sufficiently high tensile stress is built along the length direction to align the polymer chains and multiscale fibrous structures (from nano- to submicro- to microscale) are spontaneously formed in the bulk material, which are well-retained in the reswollen gel. The method is useful for relatively rigid polymers (such as alginate and cellulose), which are susceptible to mechanical signal. By controlling the drying with or without prestretching, the degree of alignment, size of superstructures, and the strength of supramolecular interactions can be tuned, which sensitively influence the strength and toughness of the hydrogels. The mechanical properties are comparable with those of natural ligaments. This study provides a general strategy for designing hydrogels with highly ordered hierarchical structures, which opens routes for the development of many functional biomimetic materials for biomedical applications.

5Previously we revealed that the high toughness of double network hydrogels (DN gels) derives from the internal fracture of the brittle network during deformation, which dissipates energy as sacrificial bonds. In this study, we intend to elucidate the detailed internal fracture process of DN gels. We quantitatively analysed the tensile hysteresis and re-swelling behaviour of a DN gel that shows a well-defined necking and strain hardening, and obtained the following new findings: 1) Fracture of the 1 st network PAMPS 10 starts far below the yielding strain, and 90% of the initially load-bearing PAMPS chains already breaks at the necking point.2) The dominant internal fracture process occurs in the necking and hardening region although the softening mainly occurs before necking.3) The internal fracture efficiency is very high, 85% of the work is used for the internal fracture and 9% of all PAMPS chains break at sample failure. 4) The internal fracture is anisotropic, fracture occurs preferentially perpendicular to the tensile direction than 15 other two directions, but the fracture anisotropy decreases in the hardening region. Result 1) and 2) is in agreement with a hierarchical structural model of PAMPS network. Based on these findings, we present a revised description of the fracture process of DN gels.

We elucidate why the anomalous high strength of double network gels is obtained when the second network is polymerized without any cross-linkers. We have synthesized truly independent-DN gels (named "t-DN" gels), which do not have any covalent bonds between the first and the second networks, and showed that the t-DN gels cannot be toughened by the un-cross-linked second network. It means that the high strength of usual DN gels without the cross-linker of the second network is actually achieved by the interconnection between the two networks through covalent bonds (so usual DN gels were named "c-DN" gels). Further, we found that the t-DN gels become stronger than the c-DN gels when the second network is loosely cross-linked. As the t-DN gels have a more simple structure than the c-DN gels, we expect that the toughening mechanism of DN gels will be clarified by studying the t-DN gels in the future.

Implanting hydroxyapatite-mineralized tough hydrogel into osteochondral defects of rabbits, osteogenesis spontaneously penetrates into the gel matrix owing to the semi-permeablility of the hydrogel. The gradient layer (around 40 μm thick) contributes quite strong bonding of the gel to bone. This is the first success in realizing the robust osteointegration of tough hydrogels, and the method is simple and feasible for practical use