Recent twists in photoactuation and photoalignment control

The design of functional and stimuli-responsive materials is among the key goals of modern materials science

Enhanced photoinduced birefringence in polymer-dye complexes: Hydrogen bonding makes a difference

The authors demonstrate that photoinduced birefringence in azo-dye-doped polymers is strongly enhanced by hydrogen bonding between the guest molecules and the polymer host. The primary mechanism behind the enhancement is the possibility to use high dye doping levels compared to conventional guest-host systems because dye aggregation is restrained by hydrogen bonding. Moreover, hydrogen bonding reduces the mobility of the guest molecules in the polymer host leading to a larger fraction of the induced birefringence to be preserved after the excitation light has been turned off.Peer reviewe

Optically Controlled Latching and Launching in Soft Actuators

Snapping is an abrupt reaction, in which mechanical instability allows the structure to rapidly switch from one stabilized form to another. Snapping is attained through a sudden release of prestored elastic energy. It is perfected by natural species to enhance their preying, locomotion, and reproduction abilities. Recent developments in responsive materials research has allowed the realization of bioinspired snappers and rapidly moving soft robots triggered by external stimuli. However, it remains a grand challenge to reversibly and accurately control the snapping dynamics in terms of, e.g., onset timing and speed of motion. Here, a facile method to obtain light-fueled snapping-like launching with precise control over the elastic energy released and the onset timing is reported. The elastic energy is prestored in a light-responsive liquid crystal elastomer actuator, and the launching event is dictated by releasing the energy through a photothermally induced crystal-to-liquid transition of a liquid-crystalline adhesive latch. The method provides manual control over the amount of prestored energy, motion speed upon multiple launching events, and enables demonstrations such as jumping and catapult motions in soft robots and concerted motions of multiple launchers. The results provide a practical solution for controlled fast motions in soft small-scale robotics.publishedVersionPeer reviewe

Optically controlled grasping-slipping robot moving on tubular surfaces

Stimuli-responsive polymers provide unmatched opportunities for remotely controlled soft robots navigating in complex environments. Many of the responsive-material-based soft robots can walk on open surfaces, with movement directionality dictated by the friction anisotropy at the robot-substrate interface. Translocation in one-dimensional space such as on a tubular surface is much more challenging due to the lack of efficient friction control strategies. Such strategies could in long term provide novel application prospects in, e.g. overhaul at high altitudes and robotic operation within confined environments. In this work, we realize a liquid-crystal-elastomer-based soft robot that can move on a tubular surface through optical control over the grasping force exerted on the surface. Photoactuation allows for remotely switched gripping and friction control which, together with cyclic body deformation, enables light-fueled climbing on tubular surfaces of glass, wood, metal, and plastic with various cross-sections. We demonstrate vertical climbing, moving obstacles along the path, and load-carrying ability (at least 3 × body weight). We believe our design offer new prospects for wirelessly driven soft micro-robotics in confined spacing.publishedVersionPeer reviewe

The Halogen Bond

The halogen bond occurs when there is evidence of a net attractive interaction between an electrophilic region associated with a halogen atom in a molecular entity and a nucleophilic region in another, or the same, molecular entity. In this fairly extensive review, after a brief history of the interaction, we will provide the reader with a snapshot of where the research on the halogen bond is now, and, perhaps, where it is going. The specific advantages brought up by a design based on the use of the halogen bond will be demonstrated in quite different fields spanning from material sciences to biomolecular recognition and drug design

Reconfiguring Gaussian Curvature of Hydrogel Sheets with Photoswitchable Host–Guest Interactions

Photoinduced shape morphing has implications in fields ranging from soft robotics to biomedical devices. Despite considerable effort in this area, it remains a challenge to design materials that can be both rapidly deployed and reconfigured into multiple different three-dimensional forms, particularly in aqueous environments. In this work, we present a simple method to program and rewrite spatial variations in swelling and, therefore, Gaussian curvature in thin sheets of hydrogels using photoswitchable supramolecular complexation of azobenzene pendent groups with dissolved α-cyclodextrin. We show that the extent of swelling can be programmed via the proportion of azobenzene isomers, with a 60% decrease in areal swelling from the all trans to the predominantly cis state near room temperature. The use of thin gel sheets provides fast response times in the range of a few tens of seconds, while the shape change is persistent in the absence of light thanks to the slow rate of thermal cis–trans isomerization. Finally, we demonstrate that a single gel sheet can be programmed with a first swelling pattern via spatially defined illumination with ultraviolet light, then erased with white light, and finally redeployed with a different swelling pattern

Surface-Relief Gratings in Halogen-Bonded Polymer–Azobenzene Complexes: A Concentration-Dependence Study

In recent years, supramolecular complexes comprising a poly(4-vinylpyridine) backbone and azobenzene-based halogen bond donors have emerged as a promising class of materials for the inscription of light-induced surface-relief gratings (SRGs). The studies up to date have focused on building supramolecular hierarchies, i.e., optimizing the polymer–azobenzene noncovalent interaction for efficient surface patterning. They have been conducted using systems with relatively low azobenzene content, and little is known about the concentration dependence of SRG formation in halogen-bonded polymer–azobenzene complexes. Herein, we bridge this gap, and study the concentration dependence of SRG formation using two halogen-bond-donating azobenzene derivatives, one functionalized with a tetrafluoroiodophenyl and the other with an iodoethynylphenyl group. Both have been previously identified as efficient molecules in driving the SRG formation. We cover a broad concentration range, starting from 10 mol % azobenzene content and going all the way up to equimolar degree of complexation. The complexes are studied as spin-coated thin films, and analyzed by optical microscopy, atomic force microscopy, and optical diffraction arising during the SRG formation. We obtained diffraction efficiencies as high as 35%, and modulation depths close to 400 nm, which are significantly higher than the values previously reported for halogen-bonded polymer–azobenzene complexes

Halogen bonding enhances nonlinear optical response in poled supramolecular polymers

We demonstrate that halogen bonding strongly enhances the nonlinear optical response of poled supramolecular polymer systems. We compare three nonlinear optical chromophores with similar electronic structures but different bond-donating units, and show that both the type and the strength of the noncovalent interaction between the chromophores and the polymer matrix play their own distinctive roles in the optical nonlinearity of the systems

Coordination networks incorporating halogen-bond donor sites and azobenzene groups

Two Zn coordination networks, {[Zn(1)(Py)(2)](2)(2-propanol)}(n) (3) and {[Zn(1)(2)(Bipy)(2)](DMF)(2)}(n) (4), incorporating halogen-bond (XB) donor sites and azobenzene groups have been synthesized and fully characterized. Obtaining 3 and 4 confirms that it is possible to use a ligand wherein its coordination bond acceptor sites and XB donor sites are on the same molecular scaffold (i.e., an aromatic ring) without interfering with each other. We demonstrate that XBs play a fundamental role in the architectures and properties of the obtained coordination networks. In 3, XBs promote the formation of 2D supramolecular layers, which, by overlapping each other, allow the incorporation of 2-propanol as a guest molecule. In 4, XBs support the connection of the layers and are essential to firmly pin DMF solvent molecules through I center dot center dot center dot O contacts, thus increasing the stability of the solvated systems

Liquid Crystal Networks Meet Water : It's Complicated!

Soft robots are composed of compliant materials that facilitate high degrees of freedom, shape-change adaptability, and safer interaction with humans. An attractive choice of material for soft robotics is crosslinked networks of liquid crystal polymers (LCNs), as they are responsive to a wide variety of external stimuli and capable of undergoing fast, programmable, complex shape morphing, which allows for their use in a wide range of soft robotic applications. However, unlike hydrogels, another popular material in soft robotics, LCNs have limited applicability in flooded or aquatic environments. This can be attributed not only to the poor efficiency of common LCN actuation methods underwater but also to the complicated relationship between LCNs and water. In this review, the relationship between water and LCNs is elaborated and the existing body of literature is surveyed where LCNs, both hygroscopic and non-hygroscopic, are utilized in aquatic soft robotic applications. Then the challenges LCNs face in widespread adaptation to aquatic soft robotic applications are discussed and, finally, possible paths forward for their successful use in aquatic environments are envisaged.Peer reviewe