Amphibious Nastic Hydrogel Based on the Tropic Movement of Gelatin and Its Opposite Phase Transition to PNIPAm.

Mimicking the anisotropic structure and environmental adaptation of organisms in nature remains a key objective in the field of hydrogels. However, it has been very challenging due to complex fabrication and confined application only in water. Here, we demonstrate a new strategy of spontaneous fabrication of an anisotropic hydrogel based on our finding in the tropic movement of gelatin toward the Teflon template. The obtained hydrogel exhibits fast response and recovery under temperature stimuli both in aqueous and non-aqueous environments, making use of the approximate transition temperature and opposite phase transition behavior of gelatin and poly(N-isopropylacrylamide) (PNIPAm). Its recovery performance in water is more than 50 times faster than that of the PNIPAm hydrogel. Furthermore, the PNIPAm/gelatin hydrogel can achieve 3D complex deformations, stealth deformation, erasable and reprogrammed surface patterning, and multistage encryption by simply modulating the location and shape of gelatin to achieve an anisotropic structure. The work provides a simple and versatile way to obtain an anisotropic hydrogel with a definite and predictable structure, which is demonstrated across a range of different monomers. It improves the responsive performance and broadens the hydrogel application to the non-aqueous environment. Additionally, this tropic movement of gelatin can be extended for the design of new types of anisotropic materials and thus endows the materials with diverse functionality.

PEG-Induced Controllable Thin-Thickness Gradient and Water Retention: A Simple Way to Programme Deformation of Hydrogel Actuators.

Building the differential growth through the thickness is a promising and challenging approach to design the morphing structures of hydrogel actuators. Besides retaining the size of the hydrogel actuators under environmental stimuli still remains a big challenge. Herein, a facile and universal approach is developed to address both issues by introducing PEG during the polymerization of N-isopropylacrylamide (NIPAm) via one step method using asymmetric mold. Both composition gradient and pore gradient are obtained in micro level along the thickness direction of the final hydrogel, while thin-thickness gradient in macro level. The thickness gradient and water retention can be controllably adjusted by changing PEG concentration. The introduction of PEG effectively improves both responsive and non-shrunken performance by the interaction with PNIPAm. The resultant anisotropic PNIPAm/PEG hydrogel respond quickly and reach maximum deformation (360°) within 10 s at low temperature (40 °C). The various 3D shape and biomimetic movement can be programmed by simply controlling the PEG concentration and mold shape. This strategy can provide new insights into the design intelligent soft materials with 3D morphing for bioinspired and biomedical applications.

Multiresponsive Color-Changing and Tough Hydrogels Enabled by Self-Assembled Epoxy Oligomer Microspheres.

The fabrication process of hydrogels often incorporates various strategies to achieve multiple responses and enhance strength, which always make the procedure complex and even hinder the incorporation. Here, we develop a facile and flexible method to simultaneously achieve multiresponsive color-changing and tough properties in hydrogels by introducing epoxy oligomer microspheres (DEPMS) to hydrophobic association (HA) hydrogels. DEPMS is responsive to both pH and solvents, showing color changes due to conversion to a conjugated structure. The obtained DEPMS composite hydrogels could demonstrate diverse color-changing patterns by simply adjusting the components and pH of the solvents. Meanwhile, amphiphilic DEPMS helps to disperse hydrophobic regions of the HA hydrogel, resulting in more uniform cross-linking and thereby contributing to the enhanced mechanical properties. The tensile strength and toughness of the composite hydrogels could be easily adjusted and reach 1.00 MPa and 11.18 MJ m-3, respectively. This work provides an approach to the design of multiple responsive and tough hydrogels while offering insights into the recycling of waste epoxy resins.

Gradient hydrogel actuator with fast response and self-recovery in air.

The driving principle of a thermal-responsive hydrogel that loses water at high temperature and absorbs water at low temperature limits its application in an aqueous environment. Here, a gradient hydrogel actuator was developed by introducing sodium hyaluronate into poly(N-isopropylacrylamide) hydrogel by an asymmetric mold method. The hydrogel exhibited a fast response above the LCST in air and unusual self-recovery without the need for further temperature stimuli. The actuation behavior was related to conversion from free water to bound water and water retention within the gradient matrix. The self-recovery mechanism was explored. This work provides a new insight into designing bionic hydrogels applied in a non-aqueous environment.

Mechanically tunable ion-crosslinked alginate-based gradient hydrogels by electrolysis-electrophoresis method.

Introducing the gradient structure into ion-crosslinked polysaccharide (ICP) hydrogels is an effective strategy to expand their application scope in biomedicine and smart materials. However, fast gelation between polysaccharide and metal ion makes it difficult to construct/regulate gradient structure. Here, we developed a new method to address the issue by combining electrolysis with electrophoresis. Making use of the gradual generation of copper ions from the Cu anode and continuous migration to the cathode, a Cu2+-crosslinked sodium alginate (SA)-based hydrogel was obtained with both crosslinking density gradient and SA distribution gradient. The gradient structure can be conveniently adjusted to achieve excellent mechanical properties and delicate patterning. The electrolysis-electrophoresis method is successfully extended to versatile hydrogels by varying different metal electrodes (Fe or Zn electrodes), or different types of polysaccharides (chitosan or sodium carboxymethyl cellulose). This work opens a new insight for designing gradient ICP hydrogels and provides the potential for bionic applications.

Hierarchically spacing DNA probes on bio-based nanocrystal for spatial detection requirements.

Sterically spacing and locating functional matters at the nanoscale exert critical effects on their application, especially for the fluorescence probes whose aggregation causes emission quenching. Here we achieved a hierarchical spacing strategy of DNA fluorescence probes for ion detection via locating them separately on rod-like cellulose nanocrystals (CNCs) and further isolating CNCs by pre-grafting long molecular chains. Controlling chemical structure of CNC and location degree could adjust the inter-space of DNA probes (with a molecular length of ca. 3.6 nm) in a range of 3.5-6.5 nm with a gradient about 0.2 nm. A length up to micrometer scale of the CNC nanorods was necessary to provide DNA probes with well-separated grafting locations and enough freedom, which brought a vast linear detection range from 10 nmol/L to 5 µmol/L of Hg2+ concentration. The abundant reactive sites on CNC allowed a grafting pre-location of poly (tert-butyl acrylate) (PtBA) to promote the isolation of DNA probes. Controlled radical polymerization was employed to adjust the length of PtBA molecular chains, which increased the linear sensitivity coefficient of Hg2+ detection by ca. 2.5 times. This hierarchical nanoscale spacing concept based on chemical design can hopefully conduce to the development of biosensor and medical diagnosis. A hierarchical spacing strategy was applied to separate DNA fluorescent probes on CNCs and detect ion concentration linearly. The first-level spacing was to locate probes uniformly on CNCs, obtaining a wide linear range; and the second-level spacing was to isolate CNCs with polymer, obtaining an increased linear coefficient.