Bioinspired Multiscale Mineralization: From Fundamentals to Potential Applications.

The wondrous and imaginative designs of nature have always been an inexhaustible treasure trove for material scientists. Throughout the long evolutionary process, biominerals with hierarchical structures possess some specific advantages such as outstanding mechanical properties, biological functions, and sensing performances, the formation of which (biomineralization) is delicately regulated by organic component. Provoked by the subtle structures and profound principles of nature, bioinspired functional minerals can be designed with the participation of organic molecules. Because of the designable morphology and functions, multiscale mineralization has attracted more and more attention in the areas of medicine, chemistry, biology, and material science. This review provides a summary of current advancements in this extending topic. The mechanisms underlying mineralization is first concisely elucidated. Next, several types of minerals are categorized according to their structural characteristic, as well as the different potential applications of these materials. At last, a comprehensive overview of future developments for bioinspired multiscale mineralization is given. Concentrating on the mechanism of fabrication and broad application prospects of multiscale mineralization, the hope is to provide inspirations for the design of other functional materials.

Light and Magnetism Orchestrating Aquatic Pollutant-Degradation Robots in Programmable Trajectories.

Interfacial floating robots have promising applications in carriers, environmental monitoring, water treatment, and so on. Even though, engineering smart robots with both precisely efficient navigation and elimination of water pollutants in long term remains a challenge, as the superhydrophobicity greatly lowers resistance for aquatic motion while sacrificing chemical reactivity of the surface. Here, a pollutant-removing superhydrophobic robot integrated with well-assembled iron oxide-bismuth sulfide heterojunction composite minerals, which provide both light and magnetic propulsion, and the ability of catalytic degradation, is reported. The motion velocity of the robot reaches up to 51.9 mm s-1 within only 300 ms of acceleration under the orchestration of light, and brakes rapidly (≈200-300 ms) once turn off the light. And magnetism extends the robot to work in broad range of surface tensions in any programmable trajectory. Besides, purification of polluted water is efficiently achieved in situ and the degradation efficiency exhibits eightfold enhancements under the effect of light-triggered photothermal behavior coupled with magnetic induction, overcoming the dilemma of efficient motion with catalytic superhydrophobicity. This strategy developed here provides guidelines for the explorations of high-performance smart devices.

A hydrogel gripper enabling fine movement based on spatiotemporal mineralization.

Fine tailoring of the subtle movements of a hydrogel actuator through simple methods has widespread application prospects in wearable electronics, bionic robots and biomedical engineering. However, to the best of our knowledge, this challenge is not yet completed. Inspired by the diffusion-reaction process in nature, a hydrogel gripper with the capability of fine movement was successfully prepared based on the spatiotemporal fabrication of the polypyrrole (PPY) pattern in a poly (N-isopropylacrylamide) (PNIPAM) hydrogel. The hydrogel was given gradient porous structures using a one-step UV irradiation method. Moreover, photothermal PPY patterns on the hydrogel were obtained through spatiotemporal mineralization of ferric hydroxide followed by the polymerization of pyrrole in a controllable manner. Taking advantage of the unique structures, the hydrogel gripper can not only achieve reversible grasping-releasing of substrates with the tuning of temperature (similar to that of hands), but also generate delicate movement under the irradiation of light (resembling that of finger joints). The strategy reported here is easily accessible and there is no need for sophisticated templates, therefore making it superior to other existing methods. We believe this work will provide references for the design and application of more advanced soft actuators.

Supramolecular Self-Healing Antifouling Coating for Dental Materials.

In orthodontic treatment, orthodontic appliances are prone to bacterial infections, which pose a risk to oral health. Surface modification of orthodontic appliances has been explored to improve their antifouling properties and impart antibacterial capabilities, inhibiting initial bacterial adhesion and biofilm formation. However, coatings are susceptible to damage in the complex oral environment, leading to a loss of functionality. Here, we have prepared an antifouling self-healing coating based on supramolecular bonding by employing a simple spin coating method. The presence of the hydrophilic zwitterionic trimethylamine N-oxide (TMAO) and the hydrophobic antimicrobial moieties triclosan acrylate (TCSA) imparts to the polymers an amphiphilic structure and enhances the interaction with bacteria, resulting in excellent antimicrobial activity and surface antifouling properties. The multiple hydrogen bonds of ureido-pyrimidinone methacrylate (UPyMA) and ionic interactions contained in the polymers not only increased the adhesion of the coating to the material substrate (approximately 3 times) but also endowed the coating with the intrinsic self-healing ability to restore the antibiofouling properties at oral temperature and humidity. Finally, the polymer coating is biologically safe both in vitro and in vivo, showing no cytotoxic effects on cells and tissues. This research offers a promising avenue for improving the performance of orthodontic appliances and contributes to the maintenance and treatment of oral health.

Chitosan based photothermal scaffold fighting against bone tumor-related complications: Recurrence, infection, and defects.

After bone tumor resection, the severe complications including cancer recurrence, infection and extensive bone loss are still a challenge. To address this problem, a chitosan/hydroxypropyltrimethyl ammonium chloride chitosan/hydroxyapatite/black phosphorus (CS/HC/HA/BP) hybrid photothermal scaffold with a multistage photothermal strategy was developed. HC-stabilized BP endowed the scaffold with simultaneous antitumor/antibacterial properties under photothermal stimulation of <50 °C. Subsequently, excellent osteogenesis could be achieved with mild hyperthermia stimulation (∼42 °C) through up-regulating the expressions of heat shock proteins. Under NIR irradiation, the scaffold could eliminate 95 % of osteosarcoma cells as well as 97 % of E. coli and 92 % of S. aureus. The osteogenic gene expressions of ALP, COL 1A1, and OCN in photothermal group were 1.64, 1.31 and 1.27 folds higher than that of non-photothermal group in vivo, respectively. Therefore, the obtained scaffold synergized with multistage photothermal strategy was effective and a reference for the treatment of other complex diseases.

Heterogenous hydrogel mimicking the osteochondral ECM applied to tissue regeneration.

Inspired by the intricate extracellular matrix (ECM) of natural cartilage and subchondral bone, a heterogenous bilayer hydrogel scaffold is fabricated. Gelatin methacrylate (GelMA) and acryloyl glucosamine (AGA) serve as the main components in the upper layer, mimicking the chondral ECM. Meanwhile, vinylphosphonic acid (VPA) as a non-collagen protein analogue is incorporated into the bottom layer to induce the in situ biomineralization of calcium phosphate. The two heterogenous layers are effectively sutured together by the inter-diffusion between the upper and bottom layer hydrogels, together with chelation between the calcium ions and alginate added to separate layers. The interfacial bonding between the two different layers was thoroughly investigated via rheological measurements. The incorporation of AGA promotes chondrocytes to produce collagen type II and glycosaminoglycans and upregulates the expression of chondrogenesis-related genes. In addition, the minerals induced by VPA facilitate the osteogenesis of bone marrow mesenchymal stem cells (BMSCs). In vivo evaluation confirms the biocompatibility of the scaffold with minor inflammation and confirms the best repair ability of the bilayer hydrogel. This cell-free, cost-effective and efficient hydrogel shows great potential for osteochondral repair and inspires the design of other tissue-engineering scaffolds.