Polyoxazolines with a Vicinally Double-Bioactivated Terminus for Biomacromolecular Affinity Assessment.

Interactions between proteins and carbohydrates with larger biomacromolecules, e.g., lectins, are usually examined using self-assembled monolayers on target gold surfaces as a simplified model measuring setup. However, most of those measuring setups are either limited to a single substrate or do not allow for control over ligand distance and spacing. Here, we develop a synthetic strategy, consisting of a cascade of a thioesterification, native chemical ligation (NCL) and thiol-ene reaction, in order to create three-component polymer conjugates with a defined double bioactivation at the chain end. The target architecture is the vicinal attachment of two biomolecule residues to the α telechelic end point of a polymer and a thioether group at the ω chain end for fixating the conjugate to a gold sensor chip surface. As proof-of-principle studies for affinity measurements, we demonstrate the interaction between covalently bound mannose and ConA in surface acoustic wave (SAW) and surface plasmon resonance (SPR) experiments.

Direct hydroboration of B=B bonds: a mild strategy for the proliferation of B-B bonds.

Synthetic access to electron-precise boron chains is hampered by the preferential formation of nonclassical structures. The few existing strategies for this involve either strongly reducing reagents or transition-metal catalysts, both with distinct disadvantages. The synthesis of new furyl- and thienyl-substituted diborenes is presented, along with their direct hydroboration with catecholborane (CatBH) to form a new electron-precise B-B bond and a B3 chain. The reaction is diastereoselective and proceeds under mild conditions without the use of strong reducing agents or transition-metal catalysts commonly used in B-B coupling reactions.