A Bio-Based Supramolecular Adhesive: Ultra-High Adhesion Strengths at both Ambient and Cryogenic Temperatures and Excellent Multi-Reusability.

Developing high-performance and reusable adhesives from renewable feedstocks is of significance to sustainable development, yet it still remains a formidable task. Herein, castor oil, melevodopa, and iron ions are used as building blocks to construct a novel bio-based supramolecular adhesive (BSA) with outstanding adhesion performances. It is prepared through partial coordination between melevodopa functionalized castor oil and Fe3+ ions. Noncovalent interactions between adherends and the catechol unit from melevodopa contribute to reinforcing adhesion, and the metal-ligand coordination between catechol and Fe3+ ions is utilized to strengthen cohesion. By combining strong adhesion and tough cohesion, the prepared BSA achieves an adhesion strength of 14.6 MPa at ambient temperature, a record-high value among reported bio-based adhesives as well as supramolecular adhesives to the best of knowledge. It also outperforms those adhesives at cryogenic temperature, realizing another record-high adhesion strength of 9.5 MPa at -196 °C. In addition, the BSA displays excellent multi-reusability with more than 87% of the original adhesion strength remaining even after reuse for ten times. It is highly anticipated that this line of research will provide a new insight into designing bio-based adhesives with outstanding adhesion performances and excellent multi-reusability.

A Supramolecular Radical Dimer: High-Efficiency NIR-II Photothermal Conversion and Therapy.

Photothermal therapy at the NIR-II biowindow (1000-1350 nm) is drawing increasing interest because of its large penetration depth and maximum permissible exposure. Now, the supramolecular radical dimer, fabricated by N,N'-dimethylated dipyridinium thiazolo[5,4-d]thiazole radical cation (MPT.+ ) and cucurbit[8]uril (CB[8]), achieves strong absorption at NIR-II biowindow. The supramolecular radical dimer (2MPT.+ -CB[8]) showed highly efficient photothermal conversion and improved stability, thus contributing to the strong inhibition on HegG2 cancer cell under 1064 nm irradiation even penetrating through chicken breast tissue. This work provides a novel approach to construct NIR-II chromophore by tailor-made assembly of organic radicals. It is anticipated that this study provides a new strategy to achieve NIR-II photothermal therapy and holds promises in luminescence materials, optoelectronic materials, and also biosensing.

Supramolecular Radical Anions Triggered by Bacteria In†Situ for Selective Photothermal Therapy.

A supramolecular complex that can be selectively reduced to radical anions in situ by facultative anaerobic bacteria is reported. To this end, a water-soluble bifunctional monomer bearing perylene diimide was synthesized, and its supramolecular complex with cucurbit[7]uril was fabricated on the basis of host-guest complexation, which could be reduced to forming radical anions in the presence of E. coli. It was found that this supramolecular complex could display different ability of generating radical anions by facultative anaerobic and aerobic bacteria in terms of their various reductive abilities. The selective antibacterial activity of the supramolecular complex could be realized by the photothermal performance of the radical anions under near-infrared irradiation. It is anticipated that this method may lead to a novel bacteria-responsive photothermal therapy to regulate balance of bacterial flora.