Dissecting Binary and Ternary Iminoboronate Assemblies: A Calorimetric Study of Thermodynamics, Kinetics, and Allosteric Effects.

Dynamic covalent assemblies derived from ortho-boronoaldehydes, including iminoboronates and boronate esters, are key structural motifs in adaptive materials, chemical sensors, and reversible bioconjugation strategies. Herein, we report a label-free assay based on isothermal titration calorimetry that provides access to observed thermodynamic and model-derived kinetic parameters associated with assembly formation under defined experimental conditions. The assay further reveals cooperative binding between amine-based nucleophiles and diols toward ortho-boronoaldehyde derivatives, providing new insight into multicomponent dynamic covalent systems.