Stimuli‐Responsive Optical Nanomaterials

Responsive optical nanomaterials that can sense and translate various external stimuli into optical signals, in the forms of observable changes in appearance and variations in spectral line shapes, are among the most active research topics in nanooptics. They are intensively exploited within the regimes of the four classic optical phenomena—diffraction in photonic crystals, absorption of plasmonic nanostructures, as well as color‐switching systems, refraction of assembled birefringent nanostructures, and emission of photoluminescent nanomaterials and molecules. Herein, a comprehensive review of these research activities regarding the fundamental principles and practical strategies is provided. Starting with an overview of their substantial developments during the latest three decades, each subtopic discussion is led with fundamental theories that delineate the correlation between nanostructures and optical properties and the delicate research strategies are elaborated with specific attention focused on working principles and optical performances. The unique advantages and inherent limitations of each responsive optical nanoscale platform are summarized, accompanied by empirical criteria that should be met and perspectives on research opportunities where the developments of next‐generation responsive optical nanomaterials might be directed.     

Self‐Folded Gripper‐Like Architectures from Stimuli‐Responsive Bilayers

Self‐folding microgrippers are an emerging class of smart structures that have widespread applications in medicine and micro/nanomanipulation. To achieve their functionalities, these architectures rely on spatially patterned hinges to transform into 3D configurations in response to an external stimulus. Incorporating hinges into the devices requires the processing of multiple layers which eventually increases the fabrication costs and actuation complexities. The goal of this work is to demonstrate that it is possible to achieve gripper‐like configurations in an on‐demand manner from simple planar bilayers that do not require hinges for their actuation. Finite element modeling of bilayers is performed to understand the mechanics behind their stimuli‐responsive shape transformation behavior. The model predictions are then experimentally validated and axisymmetric gripper‐like shapes are realized using millimeter‐scale poly(dimethylsiloxane) bilayers that undergo differential swelling in organic solvents. Owing to the nature of the computational scheme which is independent of length scales and material properties, the guidelines reported here would be applicable to a diverse array of gripping systems and functional devices. Thus, this work not only demonstrates a simple route to fabricate functional microgrippers but also contributes to self‐assembly in general.     

Polymer‐Based Stimuli‐Responsive Recyclable Catalytic Systems for Organic Synthesis

The introduction of stimuli‐responsive polymers into the study of organic catalysis leads to the generation of a new kind of polymer‐based stimuli‐responsive recyclable catalytic system. Owing to their reversible switching properties in response to external stimuli, these systems are capable of improving the mass transports of reactants/products in aqueous solution, modulating the chemical reaction rates, and switching the catalytic process on and off. Furthermore, their stimuli‐responsive properties facilitate the separation and recovery of the active catalysts from the reaction mixtures. As a fascinating approach of the controllable catalysis, these stimuli‐responsive catalytic systems including thermoresponsive, pH‐responsive, chemo‐mechano‐chemical, ionic strength‐responsive, and dual‐responsive, are reviewed in terms of their nanoreactors and mechanisms.     

Performing Logical Operations with Stimuli‐Responsive Building Blocks

Chemical logic gates can be fabricated by synthesizing molecules that have the ability to detect external stimuli (e.g., temperature or pH) and provide logical outputs. It is, however, challenging to fabricate a system that consists of many logic gates using this method: complex molecules can be difficult to synthesize and these logic gates typically cannot be integrated together. Here, we fabricated different types of logic gates by assembling a combination of different types of stimuli‐responsive hydrogels that change their size under the influence of one type of stimulus. Importantly, the preparation of these stimuli‐responsive hydrogels is widely reported and technically simple. Through designing the geometry of the systems, we fabricated the YES, NOT, OR, AND, NOR, and NAND gates. Although the hydrogels respond to different types of stimuli, their outputs are the same: a change in size of the hydrogel. Hence, we show that the logic gates can be integrated easily (e.g., by connecting an AND gate to an OR gate). In addition, we fabricated a standalone system with the size of a normal drug tablet (i.e., a “smart tablet”) that can analyze (or diagnose) different stimuli and control the release of a chemical (or drug) via the logic gates.     

Stimuli‐Responsive Self‐Assembled DNA Nanomaterials for Biomedical Applications

Stimuli‐responsive DNA‐based materials represent a major class of remarkable functional nanomaterials for nano‐biotechnological applications. In this review, recent progress in the development of stimuli‐responsive systems based on self‐assembled DNA nanostructures is introduced and classified. Representative examples are presented in terms of their design, working principles and mechanisms to trigger the response of the stimuli‐responsive DNA system upon expose to a large variety of stimuli including pH, metal ions, oligonucleotides, small molecules, enzymes, heat, and light. Substantial in vitro studies have clearly revealed the advantages of the use of stimuli‐responsive DNA nanomaterials in different biomedical applications, particularly for biosensing, drug delivery, therapy and diagnostic purposes in addition to bio‐computing. Some of the challenges faced and suggestions for further development are also highlighted.     

Dynamic Control of Light Direction Enabled by Stimuli‐Responsive Liquid Crystal Gratings

The ability to control light direction with tailored precision via facile means is long‐desired in science and industry. With the advances in optics, a periodic structure called diffraction grating gains prominence and renders a more flexible control over light propagation when compared to prisms. Today, diffraction gratings are common components in wavelength division multiplexing devices, monochromators, lasers, spectrometers, media storage, beam steering, and many other applications. Next‐generation optical devices, however, demand nonmechanical, full and remote control, besides generating higher than 1D diffraction patterns with as few optical elements as possible. Liquid crystals (LCs) are great candidates for light control since they can form various patterns under different stimuli, including periodic structures capable of behaving as diffraction gratings. The characteristics of such gratings depend on several physical properties of the LCs such as film thickness, periodicity, and molecular orientation, all resulting from the internal constraints of the sample, and all of these are easily controllable. In this review, the authors summarize the research and development on stimuli‐controllable diffraction gratings and beam steering using LCs as the active optical materials. Dynamic gratings fabricated by applying external field forces or surface treatments and made of chiral and nonchiral LCs with and without polymer networks are described. LC gratings capable of switching under external stimuli such as light, electric and magnetic fields, heat, and chemical composition are discussed. The focus is on the materials, designs, applications, and future prospects of diffraction gratings using LC materials as active layers.