| Lanthanide-based materials with distinct optical performances have displayed great value in information storage and anticounterfeiting applications.For luminescent inks based on lanthanide-doped nanomaterials,due to the weak mechanical strength,or poor integrity of the inks,the stored information may easily be damaged under deformations.Therefore,it is of great significance to develop rare-earth fluorescent materials with high mechanical properties,strong plasticity,and deformation adaptability for information storage.In addition,inspired by a variety of structural proteins,ultra-strong adhesion under a special environment is realized via suitable molecular engineering and biomimetic recombination in the field of high-performance engineered protein adhesives.At the same time,molecular simulation contributes to a deep understanding of the internal mechanism of interfacial adhesion,offering theoretical guidance for the further design of protein adhesive systems on demand.Based on the above background,this paper mainly focuses on fabricating molecular engineering-driven rare-earth functional biomaterials,which is carried out from the following four aspects:Firstly,a series of lanthanide-based luminescent organogels with ultrastrong mechanical performance and outstanding plasticity are developed for patterned information storage and encryption applications.The organogels possessing outstanding mechanical properties and tunable luminescent colors are prepared by molecular engineering of electrostatic and coordinative interactions between natural DNA,synthetic ligands,and rare-earth(RE)ions.The organogel-REs show an ultrastrong breaking strength of 80 MPa.A series of applications with both information storage and encryption,such as self-information patterns,quick response(QR)codes,and barcodes,are successfully demonstrated.Secondly,addressing the problems of inherent weak adhesion strength and limited environmental tolerance of supramolecular adhesives,we develop a new type of temperature-resistant crown-ether-protein(CEP)adhesive by harnessing synergistic host-guest molecular interactions between engineered crown ether and protein building blocks.The outputs of CEP adhesive demonstrate ultrahigh shearing adhesion strength of ≈22 MPa over a wide temperature range from-196 to 200℃,superior to other reported supramolecular or polymeric adhesives.The temperature-induced phase transition and internal bound water stabilized the system and led to superb adhesion under extreme conditions.Combining molecular engineering,we next fabricate new biosynthetic protein bioadhesives with superior adhesion performance by simply mixing engineered protein and aldehyde crosslinkers.Lysine-rich engineered proteins are de novo designed and massively biosynthesized to instantaneously reacted with aldehyde crosslinkers to realize in situ strong adhesion.The obtained LEP bioadhesives show an ultra-high adhesion strength of～101.6 kPa on porcine skin,outperforming extant clinical bioglues.In addition,they possess super biocompatibility,flexibility,biodegradability,and compliance to the tissues.Benefiting from the robust and instantaneous adhesion properties,the LEP bioadhesives are qualified for dynamic wound closure,facilitating wound repair,and noncompressible hemorrhage.Importantly,they could be industrially encapsulated into custom-made cartridge delivery tubes at low cost for clinical use.Finally,to circumvent the inherent biotoxicity of most aldehyde crosslinking agents,we develop fully extracellular matrix-derived bioadhesives with complete biocompatibility for wound repair and bleeding control applications.The adhesive is prepared to contain 5%oxidized hyaluronic acid and 300 mg/mL LEP.Its strength reaches 70.5 kPa,superior to clinical BioGlue and cyanoacrylate.Owing to excellent adhesion and homologous biocompatibility similar to the extracellular matrix,the adhesive is also ideal for wound repair and hemostasis. |
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