Reversible Snapping of Constrained Anisotropic Hydrogels Upon Light Stimulations.

Creatures, such as Venus flytrap and hummingbirds, capable of rapid predation through snap-through transition, provide paradigms for the design of soft actuators and robots with fast actions. However, these artificial "snappers" usually need contact stimulations to trigger the flipping. Reported here is a constrained anisotropic poly(N-isopropylacrylamide) hydrogel showing fast snapping upon light stimulation. This hydrogel is prepared by flow-induced orientation of nanosheets (NSs) within a rectangular tube. The precursor containing gold nanoparticles is immediately exposed to UV light for photopolymerization to fix the ordered structure of NSs. Two ends of the slender gel are clamped to form a buckle with bistability nature, which snaps to the other side upon laser irradiation. Systematic experiments are conducted to investigate the influences of power intensity and irradiation angle of the laser, as well as thickness and buckle height of the gel, on the snapping behaviors. The fast snapping is further used to kick a plastic bead and control the switch state. Furthermore, synergetic or oscillated snapping of the gel with two buckles of opposite directions is realized by inclined irradiation of a laser or horizontal irradiation with two lasers, respectively. Such light-steered snapping of hydrogels should merit designing soft robots, energy harvests, etc.

Photo-steered rapid and multimodal locomotion of 3D-printed tough hydrogel robots.

Hydrogels are an ideal material to develop soft robots. However, it remains a grand challenge to develop miniaturized hydrogel robots with mechanical robustness, rapid actuation, and multi-gait motions. Reported here is a facile strategy to fabricate hydrogel-based soft robots by three-dimensional (3D) printing of responsive and nonresponsive tough gels for programmed morphing and locomotion upon stimulations. Highly viscoelastic poly(acrylic acid-co-acrylamide) and poly(acrylic acid-co-N-isopropyl acrylamide) aqueous solutions, as well as their mixtures, are printed with multiple nozzles into 3D constructs followed by incubation in a solution of zirconium ions to form robust carboxyl-Zr4+ coordination complexes, to produce tough metallo-supramolecular hydrogel fibers. Gold nanorods are incorporated into ink to afford printed gels with response to light. Owing to the mechanical excellence and small diameter of gel fibers, the printed hydrogel robots exhibit high robustness, fast response, and agile motions when remotely steered by dynamic light. The design of printed constructs and steering with spatiotemporal light allow for multimodal motions with programmable trajectories of the gel robots. The hydrogel robots can walk, turn, flip, and transport cargos upon light stimulations. Such printed hydrogels with good mechanical performances, fast response, and agile locomotion may open opportunities for soft robots in biomedical and engineering fields.

Magneto-Orientation of Magnetic Double Stacks for Patterned Anisotropic Hydrogels with Multiple Responses and Modulable Motions.

Reported here is a multi-response anisotropic poly(N-isopropylacrylamide) hydrogel developed by using a rotating magnetic field to align magnetic double stacks (MDSs) that are fixed by polymerization. The magneto-orientation of MDSs originates from the unique structure with γ-Fe2 O3 nanoparticles sandwiched by two silicate nanosheets. The resultant gels not only exhibit anisotropic optical and mechanical properties but also show anisotropic responses to temperature and light. Gels with complex ordered structures of MDSs are further devised by multi-step magnetic orientation and photolithographic polymerization. These gels show varied birefringence patterns with potentials as information materials, and can deform into specific configurations upon stimulations. Multi-gait motions are further realized in the patterned gel through dynamic deformation under spatiotemporal light and friction regulation by imposed magnetic force. The magneto-orientation assisted fabrication of hydrogels with anisotropic structures and additional functions should bring opportunities for gel materials in biomedical devices, soft actuators/robots, etc.

Patterned Electrode Assisted One-Step Fabrication of Biomimetic Morphing Hydrogels with Sophisticated Anisotropic Structures.

Anisotropic structures are ubiquitous in nature, affording fascinating morphing behaviors. Biomimetic morphing materials can be developed by spatially controlling the orientations of molecules or nanofillers that produce anisotropic responses and internal stresses under external stimuli. However, it remains a serious challenge to fabricate materials with sophisticated anisotropic architectures. Here, a facile strategy to fabricate morphing hydrogels with elaborately ordered structures of nanosheets, which are oriented under distributed electric field and immobilized by polymerization to form a poly(N-isopropylacrylamide) matrix, is proposed. Diverse sophisticated anisotropic structures are obtained by engineering the electric field through the patterns and relative locations of the electrodes. Upon heating, the monolithic hydrogels with through-thickness and/or in-plane gradients in orientation of the nanosheets deform into various three-dimensional configurations. After incorporating gold nanoparticles, the hydrogels become photoresponsive and capable of programmable motions, for example, dynamic twisting and flipping under spatiotemporal stimuli. Such a strategy of using patterned electrodes to generate distributed electric field should be applicable to systems of liquid crystals or charged particles/molecules to direct orientation or electrophoresis and form functional structures. The biomimetically architectured hydrogels would be ideal materials to develop artificial muscles, soft actuators/robots, and biomedical devices with versatile applications.

Photoregulated Gradient Structure and Programmable Mechanical Performances of Tough Hydrogels with a Hydrogen-Bond Network.

Gradient materials exist widely in natural living organisms, affording fascinating biological and mechanical properties. However, the synthetic gradient hydrogels are usually mechanically weak or only have relatively simple gradient structures. Here, we report on tough nanocomposite hydrogels with designable gradient network structure and mechanical properties by a facile post-photoregulation strategy. Poly(1-vinylimidazole-co-methacrylic acid) hydrogels containing gold nanorods (AuNRs) are in a glassy state and show typical yielding and forced elastic deformation at room temperature. The gel slightly contracts its volume when the temperature is above the glass-transition temperature that results in a collapse of the chain segments and formation of denser intra- and interchain hydrogen bonds. Consequently, the mechanical properties of the gels are enhanced, when the temperature returns to room temperature. The mechanical performances of hydrogels can also be locally tuned by near-infrared light irradiation due to the photothermal effect of AuNRs. Hydrogels with arbitrary two-dimensional gradients can be facilely developed by site-specific photoirradiation. The treated and untreated regions with different stiffness and yielding stress possess construct behaviors in stretching or twisting deformations. A locally reinforced hydrogel with the kirigami structure becomes notch-insensitive and exhibits improved strength and stretchability because the treated regions ahead the cuts have better resistance to crack advancement. These tough hydrogels with programmable gradient structure and mechanics should find applications as structural elements, biological devices, etc.

Distributed Electric Field Induces Orientations of Nanosheets to Prepare Hydrogels with Elaborate Ordered Structures and Programmed Deformations.

Living organisms use musculatures with spatially distributed anisotropic structures to actuate deformations and locomotion with fascinating functions. Replicating such structural features in artificial materials is of great significance yet remains a big challenge. Here, a facile strategy is reported to fabricate hydrogels with elaborate ordered structures of nanosheets (NSs) oriented under a distributed electric field. Multiple electrodes are distributed with various arrangements in the precursor solution containing NSs and gold nanoparticles. A complex electric field induces sophisticated orientations of the NSs that are permanently inscribed by subsequent photo-polymerization. The resultant anisotropic nanocomposite poly(N-isopropylacrylamide) hydrogels exhibit rapid deformation upon heating or photoirradiation, owing to the fast switching of permittivity of the media and electric repulsion between the NSs. The complex alignments of NSs and anisotropic shape change of discrete regions result in programmed deformation of the hydrogels into various configurations. Furthermore, locomotion is realized by a spatiotemporal light stimulation that locally triggers time-variant shape change of the composite hydrogel with complex anisotropic structures. Such a strategy on the basis of the distributed electric-field-generated ordered structures should be applicable to gels, elastomers, and thermosets loaded with other anisotropic particles or liquid crystals, for the design of biomimetic/bioinspired materials with specific functionalities.

Photodirected Morphing Structures of Nanocomposite Shape Memory Hydrogel with High Stiffness and Toughness.

Shape memory hydrogels have drawn increasing attention in recent years. Practical applications require these hydrogels to have good mechanical properties as well as contactless stimulations to trigger the shape deformations. Here we report a stiff and tough shape memory hydrogel that can transform to various configurations sequentially by phototriggered site-specific deformations. Response of the shape memory hydrogel to near-infrared (NIR) light irradiation was achieved by incorporating gold nanorods (AuNRs) into the glassy gel matrix of poly(methacrylic acid-co-methacrylamide) without compromising the excellent mechanical properties. Owing to the photothermal effect of the AuNRs, the localized temperature rise led to a dramatic decrease in Young's modulus (from 200 to 2 MPa) of the prestretched hydrogel and bending deformation with a programmable direction and amplitude. More complex three-dimensional configurations can be obtained by multidirectional prestretching and shape memorizing the individual parts of the nanocomposite hydrogel. Furthermore, the AuNRs embedded in the gel were aligned along the prestretching direction, leading to anisotropic plasmon resonance. These photomediated programmable deformations of tough shape memory hydrogels should find applications in the biomedical and engineering fields.

Epidermal growth factor receptor mutations and their correlation with epidermal growth factor receptor-tyrosine kinase inhibitor therapy and association with the characteristics of patients with non-small-cell lung cancer: A meta-analysis.

BACKGROUND: Many studies have demonstrated that epidermal growth factor receptor (EGFR) mutation is associated with the response to therapy with single agent EGFR-tyrosine kinase inhibitors (EGFR-TKI) in non-small cell lung cancer (NSCLC) patients, but the extent of the effect is varied. We carried out a meta-analysis to assess the association between EGFR mutation and the efficacy of EGFR-TKI therapy and the independent predictor of EGFR mutation in order to identify who would be likely to benefit from this kind of therapy. METHODS: All literature relating to EGFR mutation and EGFR-TKI therapy was researched and carefully selected. Related variables were abstracted and the pooled odds ratio calculated after a heterogeneity test with the software, State 10. Publication bias was evaluated at the same time. RESULTS: Seventeen studies were included according to the selection criteria. We found a statistically significant higher probability of response in patients with an EGFR mutation versus wild-type (19.33, 95% CI, 13.61-27.46, P < 0.0001). Furthermore, the pooled odds ration of susceptibility to EGFR mutation among female patients compared with male patients was 3.01 (95% confidence interval (CI), 2.34-3.88 P < 0.0001), adenocarcinoma patients compared with non-adenocarcinoma patients was 5.40 (95% CI, 2.55-11.40 P < 0.0001), and non-smoker patients compared smoker patients was 19.33 (95% CI:,13.61-27.46 P < 0.0001). The publication bias analysis had no statistically significant results. CONCLUSION: Female, adenocarcinoma and non-smoker are independent predictors for the EGFR mutation. Efficacy of EGFR-TKI therapy favors patients with an EGFR mutation. Without the gene mutational analysis, patients selected for EGFR-TKI therapy should be female non-smokers with adenocarcinoma.