Exploiting the Structural Metamorphosis of Polymers to 'Wrap' Micron-Sized Spherical Objects.

There is growing interest in developing methods to 'wrap' nano- and micron-sized biological objects within films that may offer protection, enhance their stability or improve performance. We describe the successful 'wrapping' of lectin-decorated microspheres, which serve as appealing model micron-sized objects, within cross-linked polymer film. This approach utilizes polymer chains able to undergo a structural metamorphosis, from being intramolecularly cross-linked to intermolecularly cross-linked, a process that is triggered by polymer concentration upon the particle surface. Experiments demonstrate that both complementary molecular recognition and the dynamic covalent nature of the crosslinker are required for successful 'wrapping' to occur. This work is significant as it suggests that nano- and micron-sized biological objects such as virus-like particles, bacteria or mammalian cells-all of which may benefit from additional environmental protection or stabilization in emerging applications-may also be 'wrapped' by this approach.

Enhancing the kinetics of hydrazone exchange processes: an experimental and computational study.

The capacity of hydrazone bonds to readily undergo component exchange processes sees their extensive utilization in dynamic combinatorial chemistry. The kinetics of hydrazone exchange are optimal at pH ∼4.5, which limits the use of hydrazone-based dynamic combinatorial libraries, particularly for biological targets which are only stable at near-neutral pH values. It would thus be advantageous if hydrazone exchange proceeded with faster rates at pH values closer to neutral. We experimentally and computationally evaluated the hypothesis that hydrazones possessing neighbouring acidic or basic functional groups within the carbonyl-derived moitety of the hydrazone would enhance exchange rates. Our work suggests that judiciously placed N- or O-hydrogen bond acceptors within the carbonyl-derived moiety of the hydrazone stabilize transition states via hydrogen bonding interactions, providing a valuable boost to exchange kinetics at near-neutral pH values. We anticipate these findings will be of interest in dynamic combinatorial chemistry, dynamic covalent polymers/materials, functionalized nanoparticles and interlocked molecules, all of which may benefit from hydrazone exchange processes able to operate at near-neutral pH values.

Probing the Surfaces of Biomacromolecules with Polymer-Scaffolded Dynamic Combinatorial Libraries.

Methods to analyze and compare biomacromolecular surfaces are still in their relative infancy on account of the challenges involved in comparing surfaces computationally. We describe a systems chemistry approach that utilizes polymer-scaffolded dynamic combinatorial libraries to experimentally probe biomacromolecular surfaces in aqueous solution which provides feedback as to the nature of the surfaces, allowing the comparison of three globular proteins and a nucleic acid.