Robust Hydrogels from Lanthanide Nucleotide Coordination with Evolving Nanostructures for a Highly Stable Protein Encapsulation.

Metal coordination with organic ligands often produce crystalline metal-organic frameworks and sometimes amorphous nanoparticles. In this work, we explore a different type of material from the same chemistry: hydrogels. Lanthanides are chosen as the metal component because of their important technological applications and continuously tunable properties. Adenosine monophosphate (AMP) and lanthanides form two types of coordination materials: the lighter lanthanides from La3+ to Tb3+ form nanoparticles, whereas the rest heavier ones initially form nanoparticles but later spontaneously transform to hydrogels. This slow sol-to-gel transition is accompanied by heat release, as indicated by isothermal titration calorimetry. The transition is also accompanied by a morphology change from nanoparticles to nanofibers, as indicated by transmission electron microscopy. These gels are insensitive to ionic strength or temperature with excellent stability. Gelation is unique to AMP because other nucleotides or other adenine derivatives only yield nanoparticles or soluble products. Entrapment of guest molecules such as glucose oxidase is also explored, where the hydrogels allow a better enzyme activity and stability compared to nanoparticles. Further applications of lanthanide coordinated hydrogels might include biosensors, imaging agents, and drug delivery.