Chiral
plasmonic nanocrystals are promising materials for applications
in enantioselective catalysis, DNA detection, and medical diagnosis.
Herein, we demonstrate a simple and versatile strategy that produces
plasmonic nanostructures with strong chiroptical responses by a chiral
ligand mediated seeded growth approach. By modulation of the surface
coverage of chiral ligands on Au nanotriangles, propeller-like structures
with the growth of three arms on the tips of the triangles are produced
with a high anisotropy factor. Finally, these Au chiral propellers
can be used as substrates for the surface-enhanced Raman scattering
(SERS) detection of chiral biomolecules, achieving chiral differentiation
for enantiomers of biomolecules.
Precise organization of matter across multiple length scales is of particular interest because of its great potential with advanced functions and properties. Here we demonstrate a simple yet versatile strategy that enables the organization of hydrophobic nanoparticles within the covalent organic framework (COF) in an emulsion droplet. The interfacial polymerization takes place upon the addition of Lewis acid in the aqueous phase, which allows the formation of COF after a crystallization process. Meanwhile, the interaction between nanoparticles and COF is realized by the use of amine-aldehyde reactions in the nearest loci of the nanoparticles. Importantly, the competition between the nanoparticle self-assembly and interfacial polymerization allows control over the spatial distribution of nanoparticles within COF. As a general strategy, a wide variety of COF-wrapped nanoparticle assemblies can be synthesized and these hybridized nanomaterials could find applications in optoelectronics, heterogeneous catalysis and energy chemistry.
Although
self-assembly of binary nanocrystal mixtures into long-range
ordered crystalline films with tunable lattice structures are well-known,
it would be interesting to shape these binary nanocrystal supracrystals
into faceted assemblies because it potentially provides the shape-dependent
optical, electronic, and catalytic properties. Herein, we report the
self-assembly of binary nanocrystal supracrystals with faceted morphologies
from Fe3O4 and Au binary mixtures. The asymmetric
crystal parameters in AlB2-type structure, a = b > c, favors one-dimensional
(1D) self-assembly along the ⟨001⟩ direction, resulting
in the formation of supraspindles and suprarods with 20 facets. For
the symmetric cubic lattice system, like NaCl-type and NaZn13-type structures, truncated cube/octahedron with preferential exposed
facets of (100) and (111) are produced. By contrast, for another cubic
lattice of bcc-AB6, in which large nanocrystals
are ordered into body-centered-cubic (bcc) structure,
truncated rhombic dodecahedra enclosed with (110) and (100) are made.
The shape-controlled assembly of binary nanocrystal supracrystals
composed of plasmonic Au nanocrystals enables engineering the plasmonic
near field coupling in binary nanocrystal supracrystals dispersed
in water.
Although
self-assembly across multiple length scales has been well
recognized and intensively investigated in natural biological system,
the design of artificial heterostructures enabled by integrative self-assembly
is still in its infancy. Here we report a strategy toward the growth
of discrete supracrystalline heterostructures from inorganic nanocrystals
and porous organic cages (CC3-
R), which
in principle relies on the host–guest interactions between
alkyl chains coated on nanocrystals and the cavity of cage molecules.
Density functional theory calculation indicates that an attractive
energy of ∼−2 k
BT is present
between an alkyl chain and the cavity of a CC3-
R molecule, which is responsible for the assembly of nanocrystal
superlattices on the CC3-
R octahedral
crystals. Of particular interest is that, determined by the shape
of the nanocrystals, two distinct assembly modes can be controlled
at the mesoscale level, which eventually produce either a core/shell
or heterodimer supracrystalline structure. Our results highlight opportunities
for the development of such a noncovalent integrative self-assembly
not limited to a particular length scale and that could be generally
applicable for flexible integration of supramolecular systems.
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