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Organisationseinheit der BAM
Controllable covalent surface functionalization of black phosphorus (BP) remains a central challenge in the development of 2D phosphorus‐based materials. Here, we report a scalable route to synthesize biodegradable BP‐polymer hybrids and establish optimal conditions for BP production, exfoliation, and covalent modification. BP sheets, produced via optimized mechanochemical and exfoliation processes, are covalently functionalized with 2‐azido‐4,6‐dichloro‐1,3,5‐triazine via a nitrene‐mediated [2+1] cycloaddition. The reaction yields a P‐N bond, verified by advanced surface analyses and density functional theory (DFT) calculations. The conjugated triazine groups enable subsequent nucleophilic aromatic substitution reactions, providing a versatile platform for controlled post‐modification of BP surface. This covalent functionalization strategy addresses key limitations in BP surface chemistry and provides a route toward biodegradable phosphorus‐based hybrid materials. As a representative example, functionalization with linear polyglycerol sulfate produces BP‐polymer conjugates that inhibit respiratory syncytial virus (RSV) and herpes simplex virus 1 (HSV‐1) at low‐microgram‐per‐milliliter concentrations.
Graphene oxide (GO) has emerged as a promising biomaterial as it is easily and cheaply synthesized, strong, cytocompatible, osteoinductive, and has a well-characterized aqueous degradation pathway. It is also a great substrate for functionalization with biomolecules such as proteins, peptides, and small molecules that can enhance or add bioactivity. Covalent chemical linkages as opposed to typical noncovalent association methods are preferable so that the biomolecules do not quickly diffuse away or face replacement by other proteins, which is critical in long time scale applications like bone regeneration. However, covalent chemistry tends to carry a drawback of harsh reaction conditions that can damage the structure, conformation, and therefore function of a delicate biomolecule like a protein. Here, the Mitsunobu reaction is introduced as a novel method of covalently attaching proteins to graphene oxide. It features gentle reaction conditions and has the added benefit of utilizing the plentiful basal plane alcohol functionalities on graphene oxide, allowing for high yield protein functionalization. The amino acid Glycine (G), the protein bovine serum albumin (BSA), and the small molecule SVAK-12 are utilized to create the three Mitsunobu Graphene (MG) materials G-MG, BSA-MG, and SVAK-MG that demonstrate the wide applicability of this functionalization method.
Scalable covalently functionalized black phosphorus hybrids for broadspectrum virucidal activity
(2025)
At the onset of viral outbreaks, broad-spectrum antiviral materials are crucial before specific therapeutics become available. We report scalable, biodegradable black phosphorus (BP) hybrids that provide mutation-resilient virucidal protection. BP sheets, produced via an optimized mechanochemical process, are covalently functionalized with 2-azido-4,6-dichloro- 1,3,5-triazine to form P=N bonds. Fucoidan, a sulfated polysaccharide with intrinsic antiviral activity, and hydrophobic chains are then incorporated to achieve irreversible viral deactivation. The material exhibits strong antiviral inhibition and complete virucidal activity against multiple viruses, including recent severe acute respiratory syndrome coronavirus-2 (SARS-CoV-2) variants. It maintains high biocompatibility, remains effective against viral mutations, and is shelf stable for at least five month. The combination of biodegradability, scalable synthesis, and synergistic antiviral and virucidal mechanisms establishes BP-conjugates as a new class of highly efficient antivirals. They offer a broad spectrum antiviral solutions that could bridge the gap between antiviral medicines and general antiseptics.
Innovative materials are crucial for removing persistent pollutants per‐ and polyfluorinated alkyl substances (PFAS) from water. Here, a novel bifunctional reduced graphene oxide (TRGO) adsorbent is developed and characterized by advanced surface sensitive methods. Compared to pristine TRGO, the functionalized TRGO shows markedly improved PFAS removal efficiency and demonstrates strong potential for water purification applications.
