Encapsulation of
biomolecules using metal–organic frameworks
(MOFs) to form stable biocomposites has been demonstrated to be a
valuable strategy for their preservation and controlled release, which
has been however restricted to specific electrostatic surface conditions.
We present a Lewis-acid-mediated general
in situ
strategy
that promotes the spontaneous MOF growth on a broad variety of proteins,
for the first time, regardless of their surface nature. We demonstrate
that MOFs based on cations exhibiting considerable inherent acidity
such as MIL-100(Fe) enable efficient biomolecule encapsulation, including
elusive alkaline proteins previously inaccessible by the well-developed
in situ
azolate-based MOF encapsulation. Specifically, we
prove the MIL-100(Fe) scaffold for the encapsulation of a group of
proteins exhibiting very different isoelectric points (5 < pI <
11), allowing triggered release under biocompatible conditions and
retaining their activity after exposure to denaturing environments.
Finally, we demonstrate the potential of the myoglobin-carrying biocomposite
to facilitate the delivery of O
2
into hypoxic human lung
carcinoma A549 cells, overcoming hypoxia-associated chemoresistance.