Strong Protein Adhesives through Lanthanide-enhanced Structure Folding and Stack Density.

Generating strong adhesion by engineered proteins has the potential for high technical applications. Current studies of adhesive proteins are primarily limited to marine organisms, e.g., mussel adhesive proteins. Here, we present a modular engineering strategy to generate a type of exotic protein adhesives with super strong adhesion behaviors. In the protein complexes, the lanmodulin (LanM) underwent α-helical conformational transition induced by lanthanides, thereby enhancing the stacking density and molecular interactions of adhesive protein. The resulting adhesives exhibited outstanding lap-shear strength of ≈31.7 MPa, surpassing many supramolecular and polymer adhesives. The extreme temperature (-196 to 200 °C) resistance capacity and underwater adhesion performance can significantly broaden their practical application scenarios. Ex vivo and in vivo experiments further demonstrated the persistent adhesion performance for surgical sealing and healing applications.

Protein fibers with self-recoverable mechanical properties via dynamic imine chemistry.

The manipulation of internal interactions at the molecular level within biological fibers is of particular importance but challenging, severely limiting their tunability in macroscopic performances and applications. It thus becomes imperative to explore new approaches to enhance biological fibers' stability and environmental tolerance and to impart them with diverse functionalities, such as mechanical recoverability and stimulus-triggered responses. Herein, we develop a dynamic imine fiber chemistry (DIFC) approach to engineer molecular interactions to fabricate strong and tough protein fibers with recoverability and actuating behaviors. The resulting DIF fibers exhibit extraordinary mechanical performances, outperforming many recombinant silks and synthetic polymer fibers. Remarkably, impaired DIF fibers caused by fatigue or strong acid treatment are quickly recovered in water directed by the DIFC strategy. Reproducible mechanical performance is thus observed. The DIF fibers also exhibit exotic mechanical stability at extreme temperatures (e.g., -196 °C and 150 °C). When triggered by humidity, the DIFC endows the protein fibers with diverse actuation behaviors, such as self-folding, self-stretching, and self-contracting. Therefore, the established DIFC represents an alternative strategy to strengthen biological fibers and may pave the way for their high-tech applications.

Molecular Engineered Crown-Ether-Protein with Strong Adhesion over a Wide Temperature Range from -196 to 200 °C.

The inherently tenuous adhesion strength and limited environmental tolerance of supramolecular adhesives severely restrict their application scenarios. It is challenging for the development of robust adhesives with extreme temperature tolerance. Herein, we report 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 °C, superior to other established supramolecular or polymeric adhesives. The temperature-induced phase transition and internal bound water stabilized the system and led to superb adhesion under extreme conditions. Thus, this work pioneers a molecular engineering approach for the generation of adhesives with tailored applications in extreme settings.

Biosynthetic Structural Proteins with Super Plasticity, Extraordinary Mechanical Performance, Biodegradability, Biocompatibility and Information Storage Ability.

Degradable bioplastics have attracted growing interest worldwide. However, it is challenging to develop bioplastics with a simple processing procedure, strong mechanical performance, good biocompatibility, and adjustable physicochemical properties. Herein, we introduced structural proteins as building blocks and developed a simple environmentally friendly approach to fabricate diverse protein-based plastics. A cost-effective and high-level production approach was developed through batch fermentation of Escherichia coli to produce the biomaterials. These bioplastics possess super plasticity, biocompatibility, biodegradability, and high resistance to organic solvents. Their structural and mechanical properties can be precisely controlled. Besides, high density information storage and hemostatic applications were realized in the bioplastic system. The customizable bioplastics have great potential for applications in numerous fields and are capable to scale up to the industrial level.

Highly Plasticized Lanthanide Luminescence for Information Storage and Encryption Applications.

The development of new storage media to meet the demands for diverse information storage scenarios is a great challenge. Here, 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 electrostatic and coordinative interactions between natural DNA, synthetic ligands, and rare earth (RE) ions. The organogel-REs can be stretched by 180 times and show an ultrastrong breaking strength of 80 MPa. A series of applications with both information storage and encryption, such as self-information pattern, quick response (QR) code, and barcode, are successfully demonstrated by the organogel-REs. The developed information storage systems have various advantages of good processability, high stretchability, excellent stability, and versatile design of information patterns. Therefore, the organogel-RE-based information storage systems are suitable for applications under different scenarios, such as flexible devices under repeating rude operations. The advancements will enable the design and development of luminescent organogel-REs as information storage and encryption media for various scenarios.

Genetically Engineered Polypeptide Adhesive Coacervates for Surgical Applications.

Adhesive hydrogels have been developed for wound healing applications. However, their adhesive performance is impaired dramatically due to their high swelling on wet tissues. To tackle this challenge, we fabricated a new type of non-swelling protein adhesive for underwater and in vivo applications. In this soft material, the electrostatic complexation between supercharged polypeptides with oppositely charged surfactants containing 3,4-dihydroxylphenylalanine or azobenzene moieties plays an important role for the formation of ultra-strong adhesive coacervates. Remarkably, the adhesion capability is superior to commercial cyanoacrylate when tested in ambient conditions. Moreover, the adhesion is stronger than other reported protein-based adhesives in underwater environment. The ex vivo and in vivo experiments demonstrate the persistent adhesive performance and outstanding behaviors for wound sealing and healing.

A T2ex MRI Dy-based contrast agent for direct pH imaging using a ratiometric approach.

pH is a critical parameter that has found unique application in magnetic resonance imaging (MRI) mapping acidity in tissues. This study reports a series of Dy-based MR probes that show innovative T2ex features, governed by proton catalyzed events. With an increase of pH from 5.5 to 8.0, the r2ex relaxivity increased dramatically, while the r1 relaxivity remained unchanged. The resulting r2ex/r1 allowed for concentration-independent and direct mapping of physiologically relevant pH ranges.

Lanthanide-Based Photothermal Materials: Fabrication and Biomedical Applications.

Photothermal material (PTM) is an indispensable component in noninvasive photothermal therapy. There has been a growing interest due to its excellent tumor ablation performance with minimal side effects. Recently, upconversion nanoparticles (UCNPs) have been introduced to generate PTMs owing to their outstanding merits of high signal-to-noise ratio imaging, tunable spectra feature, and accurate monitoring of real temperature in tumor tissues. The combination of rare-earth materials with the photothermal effect provides a potent strategy for synergistic phototherapy, achieving the integration of diagnosis and treatment. The current text reviews the recent advances in lanthanide-based PTMs. The design, fabrication, and applications of those PTMs are discussed systematically. Challenges and perspectives regarding the development of UCNPs-based PTMs are finally presented.

Detection and Chiral Recognition of α-Hydroxyl Acid through 1 H and CEST NMR Spectroscopy Using a Ytterbium Macrocyclic Complex.

Chiral α-hydroxyl acids are of great importance in chemical synthesis. Current methods for recognizing their chirality by 1 H NMR are limited by their small chemical shift differences and intrinsic solubility problem in organic solvents. Herein, we developed three YbDO3A(ala)3 derivatives to recognize four different commercially available chiral α-hydroxyl acids in aqueous solution through 1 H NMR and chemical exchange saturation transfer (CEST) spectroscopy. The shift difference between chiral α-hydroxyl acid observed by proton and CEST NMR ranged from 15-40 and 20-40 ppm, respectively. Our work demonstrates for first time, that even one chiral center on the side-arm chain of cyclen could set the stage for rotation of the other two non-chiral side chains into a preferred position. This is ascribed to the lower energy state of the structure. The results show that chiral YbDO3A-like complexes can be used to discriminate chiral α-hydroxyl acids with a distinct signal difference.