Conspectus
Vesicle-templated nanocapsules
offer a unique combination of properties
enabled by robust shells with single-nanometer thickness containing
programmed uniform pores capable of fast and selective mass transfer.
These capsules emerged as a versatile platform for creating functional
devices, such as nanoreactors, nanosensors, and containers for the
delivery of drugs and imaging agents. Nanocapsules are synthesized
by a directed assembly method using self-assembled bilayers of vesicles
as temporary scaffolds. In this approach, hydrophobic building blocks
are loaded into the hydrophobic interior of vesicles formed from lipids
or surfactants. Pore-forming templates are codissolved with the monomers
and cross-linkers in the interior of the bilayer. The polymerization
forms a cross-linked shell with embedded pore-forming templates. Removal
of the surfactant scaffold and pore-forming templates leads to free-standing
nanocapsules with shells containing uniform imprinted nanopores. Development
of reliable and scalable synthetic methods for the modular construction
of capsules with tunable properties has opened the opportunity to
pursue practical applications of nanocapsules.
In this Account,
we discuss how unique properties of vesicle-templated
nanocapsules translate into the creation of functional nanodevices.
Specifically, we focus the conversation on applications aiming at
the delivery of drugs and imaging agents, creation of fast-acting
and selective nanoreactors, and fabrication of nanoprobes for sensing
and imaging. We present a brief overview of the synthesis of nanocapsules
with an emphasis on recent developments leading to robust synthetic
methods including the synthesis under physiological conditions and
creation of biodegradable nanocapsules. We then highlight unique properties
of nanocapsules essential for practical applications, such as precise
control of pore size and chemical environment, selective permeability,
and ultrafast transport through the pores. We discuss new motifs for
catch and release of small molecules with porous nanocapsules based
on controlling the microenvironment inside the nanocapsules, regulating
the charge on the orifice of nanopores in the shells, and reversible
synergistic action of host and guest forming a supramolecular complex
in nanocapsules. We demonstrate successful creation of fast-acting
and selective nanoreactors by encapsulation of diverse homogeneous
and nanoparticle catalysts. Due to unhindered flow of substrates and
products through the nanopores, encapsulation did not compromise catalytic
efficiency and, in fact, improved the stability of entrapped catalysts.
We present robust nanoprobes based on nanocapsules with entrapped
sensing agents and show how the encapsulation resulted in selective
measurements with fast response times in challenging conditions, such
as small volumes and complex mixtures. Throughout this Account, we
highlight the advantages of encapsulation and discuss the opportunities
for future design of nanodevices.