Alkali metal cations can inhibit non-covalent catalysis

The study concerns the effect of inorganic salts on supramolecular catalysis. The model reaction is the acid hydrolysis of the ammonium phenyl acetate derivative promoted by cucurbit[7]uril macrocycle. When salt is absent, the macrocycle is insensitive to the ionic strength of the solution, and the reaction rate linearly depends on the concentration of hydronium ions (H3O+). After the addition of inorganic salts, in particular, Na+ and K+ ions, the catalytic effect of the macrocycle is suppressed. The kinetic and binding data collected by us evidence the formation of the ternary complexes between the cations, macrocycle, and substrate, which are less prone to H3O+ attack. This type of inhibition corresponds to a rare uncompetitive model in contrast to a more common competitive one that relies on the displacement of the substrate. This study shows that special care must be taken when studying catalysis in solutions that contain metal cations, such as regular water and inorganic buffers.

UbiD domain dynamics underpins aromatic decarboxylation

The widespread UbiD enzyme family utilises the prFMN cofactor to achieve reversible decarboxylation of acrylic and (hetero)aromatic compounds. The reaction with acrylic compounds based on reversible 1,3-dipolar cycloaddition between substrate and prFMN occurs within the confines of the active site. In contrast, during aromatic acid decarboxylation, substantial rearrangement of the substrate aromatic moiety associated with covalent catalysis presents a molecular dynamic challenge. Here we determine the crystal structures of the multi-subunit vanillic acid decarboxylase VdcCD. We demonstrate that the small VdcD subunit acts as an allosteric activator of the UbiD-like VdcC. Comparison of distinct VdcCD structures reveals domain motion of the prFMN-binding domain directly affects active site architecture. Docking of substrate and prFMN-adduct species reveals active site reorganisation coupled to domain motion supports rearrangement of the substrate aromatic moiety. Together with kinetic solvent viscosity effects, this establishes prFMN covalent catalysis of aromatic (de)carboxylation is afforded by UbiD dynamics.

Catalysis with chalcogen bonds: neutral benzodiselenazole scaffolds with high-precision selenium donors of variable strength

Benzodiselenazoles are introduced for efficient anion binding and unprecedented non-covalent catalysis in the focal point of neutral selenium-based chalcogen-bond donors.