Direct Observation of Amorphous Precursor Phases in the Nucleation of Protein–Metal–Organic Frameworks

Abstract

Protein–metal–organic frameworks (p-MOFs) are a prototypical example of how synthetic biological hybrid systems can be used to develop next-generation materials. Controlling p-MOF formation enables the design of hybrid materials with enhanced biological activity and high stability. However, such control is yet to be fully realized due to an insufficient understanding of the governing nucleation and growth mechanisms in p-MOF systems. The structural evolution of p-MOFs was probed by cryo-transmission electron microscopy, revealing nonclassical pathways via dissolution–recrystallization of highly hydrated amorphous particles and solid-state transformation of a protein-rich amorphous phase. On the basis of these data, we propose a general description of p-MOF crystallization which is best characterized by particle aggregation and colloidal theory for future synthetic strategies.

Embedding Functional Biomacromolecules within Peptide‐Directed Metal–Organic Framework (MOF) Nanoarchitectures Enables Activity Enhancement

“…Theuniversality of the engineered 2D mesoporous MOF architecture for improving the activity of biohybrids was ascertained by embedding other proteins including cytochrome C( Cyt C) and glucose oxidase (GOx) into the 2D MSMOFs.Previous studies revealed that proteins with different surface charges could affect the crystallization of ZIF-8. [23,24,33] Thus,wefirst confirmed that proteins with different surface charges (Cyt Chas positive surface charge while GOx has negative surface charge) enabled to be encapsulated within a2 DM SMOFs using our approach (Figure S13). The morphological evolution, evaluated by SEM and PXRD, indicated that the biohybrids with 2D spindle-shaped layer architecture were formed through modulating the PLGA dosage (Figure S14A-S14D).…”

Embedding Functional Biomacromolecules within Peptide‐Directed Metal–Organic Framework (MOF) Nanoarchitectures Enables Activity Enhancement

“…The universality of the engineered 2D mesoporous MOF architecture for improving the activity of biohybrids was ascertained by embedding other proteins including cytochrome C (Cyt C) and glucose oxidase (GOx) into the 2D MSMOFs. Previous studies revealed that proteins with different surface charges could affect the crystallization of ZIF‐8 . Thus, we first confirmed that proteins with different surface charges (Cyt C has positive surface charge while GOx has negative surface charge) enabled to be encapsulated within a 2D MSMOFs using our approach (Figure S13).…”

Stabilization of Supramolecular Membrane Protein-Lipid Bilayer Assemblies Through Immobilization in a Crystalline Exoskeleton

“…The initial formation of an amorphous phase is consistent with what we have observed with viral nanoparticles and other proteins. 30,42,44 Importantly, compared to the control samples, we observed faster crystallization for Lp@ZIF particles (e.g. 20×16 Lp@ZIF crystallization is 15 times faster than the pure ZIF-L particles; Figures S16-S19).…”