Photothermal Control of Membrane Permeability of Microcapsules for On-Demand Release

We report the use of a simple microfluidic device for producing microcapsules with reversible membrane permeability that can be remotely controlled by application of near-infrared (NIR) light. Water-in-oil-in-water (W/O/W) double-emulsion drops were prepared to serve as templates for the production of mechanically stable microcapsules with a core–shell structure and highly uniform size distribution. A biocompatible ethyl cellulose shell was formed, containing densely packed thermoresponsive poly­(<i>N</i>-isopropylacrylamide) (pNIPAAm) particles in which gold nanorods were embedded. Irradiation with a NIR laser resulted in heating of the hydrogel particles due to the photothermal effect of the gold nanorods, which absorb at that wavelength. This localized heating resulted in shrinkage of the particles and formation of macrogaps between them and the matrix of the membrane. Large encapsulated molecules could then pass through these gaps into the surrounding fluid. As the phase transition behavior of pNIPAAm is highly reversible, this light-triggered permeability could be repeatedly switched on and off by removing the laser irradiation for sufficient time to allow the gold nanorods to cool. This reversible and remote control of permeability enabled the programmed release of encapsulants, with the time and period of the open valve state able to be controlled by adjusting the laser exposure. This system thus has the potential for spatiotemporal release of encapsulated drugs

Monolithic Photonic Crystals Created by Partial Coalescence of Core–Shell Particles

Colloidal crystals and their derivatives have been intensively studied and developed during the past two decades due to their unique photonic band gap properties. However, complex fabrication procedures and low mechanical stability severely limit their practical uses. Here, we report stable photonic structures created by using colloidal building blocks composed of an inorganic core and an organic shell. The core–shell particles are convectively assembled into an opal structure, which is then subjected to thermal annealing. During the heat treatment, the inorganic cores, which are insensitive to heat, retain their regular arrangement in a face-centered cubic lattice, while the organic shells are partially fused with their neighbors; this forms a monolithic structure with high mechanical stability. The interparticle distance and therefore stop band position are precisely controlled by the annealing time; the distance decreases and the stop band blue shifts during the annealing. The composite films can be further treated to give a high contrast in the refractive index. The inorganic cores are selectively removed from the composite by wet etching, thereby providing an organic film containing regular arrays of air cavities. The high refractive index contrast of the porous structure gives rise to pronounced structural colors and high reflectivity at the stop band position

Colloidal Photonic Crystals toward Structural Color Palettes for Security Materials

Self-assembly of monodisperse colloidal particles into regular lattices has provided relatively simple and economical methods to prepare photonic crystals. The photonic stop band of colloidal crystals appears as opalescent structural colors, which are potentially useful for display devices, colorimetric sensors, and optical filters. However, colloidal crystals have low durability, and an undesired scattering of light makes the structures white and translucent. Moreover, micropatterning of colloidal crystals usually requires complex molding procedures, thereby limiting their practical applications. To overcome such shortcomings, we develop a pragmatic and amenable method to prepare colloidal photonic crystals with high optical transparency and physical rigidity using photocurable colloidal suspensions. The colloidal particles dispersed in a photocurable medium crystallized during capillary force-induced infiltration into a slab, and subsequent photopolymerization of the medium permanently solidifies the structures. Furthermore, conventional photolithography enables micropatterning of the crystal structures. The low index contrast between particles and matrix results in high transparency of the resultant composite structures and narrow reflection peaks, thereby enabling structural color mixing through the overlapping of distinct layers of the colloidal crystals. Multiple narrow peaks in the spectrum provide high selectivity in optical identification, thereby being potentially useful for security materials

Durable Plasmonic Cap Arrays on Flexible Substrate with Real-Time Optical Tunability for High-Fidelity SERS Devices

Active tunable plasmonic cap arrays were fabricated on a flexible stretchable substrate using a combination of colloidal lithography, lift-up soft lithography, and subsequent electrostatic assembly of gold nanoparticles. The arrangement of the plasmonic caps could be tuned under external strain to deform the substrate in reversible. Real-time variation in the arrangement could be used to tune the optical properties and the electromagnetic field enhancement, thereby a proving a promising mechanism for optimizing the SERS sensitivity

Shape Control of Ag Nanostructures for Practical SERS Substrates

Large-area, highly ordered, Ag-nanostructured arrays with various geometrical features were prepared for use as surface-enhanced Raman scattering (SERS)-active substrates by the self-assembly of inorganic particles on an SU-8 surface, followed by particle embedding and Ag vapor deposition. By adjusting the embedding time of the inorganic particles, the size of the Ag nanogap between the geometrically separated hole arrays and bowl-shaped arrays could be controlled in the range of 60 nm to 190 nm. More importantly, the SU-8 surface was covered with hexagonally ordered nanopillars, which were formed as a result of isotropic dry etching of the interstices, leading to triangular-shaped Ag plates on nanopillar arrays after Ag vapor deposition. The size and sharpness of the triangular Ag nanoplates and nanoscale roughness of the bottom surface were adjusted by controlling the etching time. The potential of the various Ag nanostructures for use as practical SERS substrates was verified by the detection of a low concentration of benzenethiol. Finite-difference time-domain (FDTD) methodology was used to demonstrate the SERS-activities of these highly controllable substrates by calculating the electric field intensity distribution on the metallic nanostructures. These substrates, with high sensitivity and simple shape-controllability, provide a practical SERS-based sensing platform

Freestanding and Arrayed Nanoporous Microcylinders for Highly Active 3D SERS Substrate

Surface-enhanced Raman scattering (SERS) has been considered as one of the most promising tools for molecular analysis. To develop practical platforms, a variety of nanoparticles and two-dimensional (2D) nanostructures have been prepared. However, low signal intensity or slow binding kinetics in conventional approaches limits their applications. To overcome these shortcomings, production and usage of three-dimensional (3D) nanostructures remain an important yet unmet need. In this paper, we report novel and effective SERS-active materials by fabricating hierarchically structured SiO₂ microcylinders decorated with gold nanoparticles. In order to fully develop 3D nanostructures, while maintaining fast diffusion of analyte molecules, we used self-assembled nanostructures of block-copolymers (BCPs) confined in the microholes of an imprinting mold; the BCPs could provide a template for producing 3D nanostructure composed of nanofibers with sub-100 nm diameter through their microphase separation, whereas the imprinting technique provided cylindrical geometry for the local confinement of the BCPs. Microcylinders with nanodomains were then transformed into microcylinders with 3D nanopores via reactive-ion etching and, subsequently, their nanopores were decorated by gold nanoparticles. The resultant 3D nanopores enable a high loading of gold nanoparticles and formation of abundant hot spots and microcylinders facilitate the fast diffusion of analyte molecules through the nanopores, resulting in significant enhancement of SERS intensity