Surface Topographical Engineering of Chiral Au Nanocrystals with Chiral Hot Spots for Plasmon-Enhanced Chiral Discrimination.

Surface roughness in chiral plasmonic nanostructures generates asymmetrical localized electromagnetic fields, which hold great promise for applications in chiral recognition, chiroptical spectroscopic sensing, and enantioselective photocatalysis. In this study, we develop a surface topographical engineering approach to precisely manipulate the surface structures of chiral Au nanocrystals. Through carefully controlling the amounts of l- or d-cystine (Cys) and the seed solution in the growth process, we successfully synthesize chiral Au nanocrystals with highly disordered, ordered, and less ordered wrinkled surfaces. An underlying principle governing the relationship between surface roughness, orderliness, and chiroptical response is also proposed. More importantly, the chiral ordered wrinkles on the surfaces of the nanocrystals generate asymmetrical localized electronic fields with enhanced intensity, which achieve excellent plasmon-enhanced chiral discrimination ability for penicillamine (Pen) enantiomers. This work offers exciting prospects for manipulating the surface structures of chiral nanocrystals and designing highly sensitive plasmon-enhanced enantioselective sensors with chiral hot spots.

Synthetic Strategies for Polymer Particles with Surface Concavities.

Over the past decade or so, there has been increasing interest in the synthesis of polymer particles with surface concavities, which mainly include golf ball-like, dimpled and surface-wrinkled polymer particles. Such syntheses generally can be classified into direct polymerization and post-treatment on preformed polymer particles. This review aims to provide an overview of the synthetic strategies of such particles. Some selected examples are given to present the formation mechanisms of the surface concavities. The applications and future development of these concave polymer particles are also briefly discussed.

Elastic Plasmonic-Enhanced Fabry-Pérot Cavities with Ultrasensitive Stretching Tunability.

The emerging stretchable photonics field faces challenges, like the robust integration of optical elements into elastic matrices or the generation of large optomechanical effects. Here, the first stretchable plasmonic-enhanced and wrinkled Fabry-Pérot (FP) cavities are demonstrated, which are composed of self-embedded arrays of Au nanostructures at controlled depths into elastomer films. The novel self-embedding process is triggered by the Au nanostructures' catalytic activity, which locally increases the polymer curing rate, thereby inducing a mechanical stress that simultaneously pulls the Au nanostructures into the polymer and forms a wrinkled skin layer. This geometry yields unprecedented optomechanical effects produced by the coupling of the broad plasmonic modes of the Au nanostructures and the FP modes, which are modulated by the wrinkled optical cavity. As a result, film stretching induces drastic changes in both the spectral position and intensity of the plasmonic-enhanced FP resonances due to the simultaneous cavity thickness reduction and cavity wrinkle flattening, thus increasing the cavity finesse. These optomechanical effects are exploited to demonstrate new strain-sensing approaches, achieving a strain detection limit of 0.006%, i.e., 16-fold lower than current optical strain-detection schemes.

Reconfigurable Micro- and Nano-Structured Camouflage Surfaces Inspired by Cephalopods.

Wrinkled surfaces and materials are found throughout the natural world in various plants and animals and are known to improve the performance of emerging optical and electrical technologies. Despite much progress, the reversible post-fabrication tuning of wrinkle sizes and geometries across multiple length scales has remained relatively challenging for some materials, and the development of comprehensive structure-function relationships for optically active wrinkled surfaces has often proven difficult. Herein, by drawing inspiration from natural cephalopod skin and leveraging methodologies established for artificial adaptive infrared platforms, we engineer systems with hierarchically reconfigurable wrinkled surface morphologies and dynamically tunable visible-to-infrared spectroscopic properties. Specifically, we demonstrate architectures for which mechanical actuation changes the surface morphological characteristics; modulates the reflectance, transmittance, and absorptance across a broad spectral window; controls the specular-to-diffuse reflectance ratios; and alters the visible and thermal appearances. Moreover, we demonstrate the incorporation of these architectures into analogous electrically actuated appearance-changing devices that feature competitive figures of merit, such as reasonable maximum areal strains, rapid response times, and good stabilities upon repeated actuation. Overall, our findings constitute another step forward in the continued development of cephalopod-inspired light- and heat-manipulating systems and may facilitate advanced applications in the areas of sensing, electronics, optics, soft robotics, and thermal management.

Biocompatible fluorinated wrinkled hydrogel films with antimicrobial activity.

Surface-modified hydrogel films were designed to control the bacterial colonization on their surface and to promote cell proliferation through the gradual insertion of highly hydrophobic functional monomers. These hydrogel films were deposited via spin-coating technique, using muscovite mica as a substrate. These samples were then exposed to different external stimuli to produce wrinkled patterns. The relationship between the monomers which compose the hydrogel, was varied to alter the hydrophobic/hydrophilic balance of the final composite. Contact angle and confocal Raman spectroscopy measurements were carried out to characterize the surface and the bulk of the hydrogel film. Cell proliferation and antimicrobial tests were performed using premyoblastic murine cells (C2C12-GFP) and RAW 264.7 (ATCC® TIB-71) macrophagic cell lines, and also for bacteria strains, Staphylococcus aureus and Escherichia coli. The results indicate that the inclusion of the TFPMA produces an increase in cell proliferation, together with a decrease in living bacterial colonies after 48 h, both for Gram-positive or Gram-negative species.