Self-Assembly of Two-Dimensional Nanosheets Induced by Interfacial Polyionic Complexation

Significant progress has been made during the past decade in preparing nanosheets from a wide range of materials, which are actively pursued for various applications such as energy storage, catalysis, sensing, and membranes. One of the next critical challenges is developing a robust and versatile assembly method which allows construction of the nanosheets into functional structures tailored for each specific purpose. An interesting characteristic of nanosheets is that they often behave as charged macromolecules and thus can readily interact with an oppositely charged polyelectrolyte to form a stable complex. In this report, we demonstrate how such a complexation process could be utilized for directing the self-assembly of nanosheets. By confining the nanosheet–polyelectrolyte complexation at air–liquid or liquid–liquid interfaces, the nanosheets are successfully assembled into various mesoscale architectures including fibers, capsules, and films. Furthermore, incorporation of additional components such as nanoparticles or small molecules can be easily achieved for further tailoring of material properties. This novel assembly method opens a pathway to many useful nanosheet superstructures and may be further extended to other types of nanomaterials in general

Integration of Porous Coordination Polymers and Gold Nanorods into Core–Shell Mesoscopic Composites toward Light-Induced Molecular Release

Besides conventional approaches for regulating in-coming molecules for gas storage, separation, or molecular sensing, the control of molecular release from the pores is a prerequisite for extending the range of their application, such as drug delivery. Herein, we report the fabrication of a new porous coordination polymer (PCP)-based composite consisting of a gold nanorod (GNR) used as an optical switch and PCP crystals for controlled molecular release using light irradiation as an external trigger. The delicate core–shell structures of this new platform, composed of an individual GNR core and an aluminum-based PCP shell, were achieved by the selective deposition of an aluminum precursor onto the surface of GNR followed by the replication of the precursor into aluminum-based PCPs. The mesoscopic structure was characterized by electron microscopy, energy dispersive X-ray elemental mapping, and sorption experiments. Combination at the nanoscale of the high storage capacity of PCPs with the photothermal properties of GNRs resulted in the implementation of unique motion-induced molecular release, triggered by the highly efficient conversion of optical energy into heat that occurs when the GNRs are irradiated into their plasmon band. Temporal control of the molecular release was demonstrated with anthracene as a guest molecule and fluorescent probe by means of fluorescence spectroscopy