Mechanical Properties of Low-Molecular-Weight Peptide Hydrogels Improved by Thiol-Ene Click Chemistry.

Low-molecular-weight peptide hydrogels can be formed by self-assembly through weak interactions, but the application of the hydrogel is influenced by its weak mechanical properties. Therefore, it is important to construct low-molecular-weight peptide hydrogels with excellent mechanical properties. In this work, we designed the pentapeptide molecule Fmoc-FFCKK-OH (abbreviated as FFCKK) with a sulfhydryl group, and another low-molecular-weight cross-linker N,N'-methylenebis(acrylamide) (MBA) was introduced to construct a hydrogel with excellent mechanical properties. The secondary structure change process of FFCKK and the assembly mechanism of hydrogel were analyzed using theoretical calculations and experimental characterizations. The occurrence of thiol-ene click chemistry provides covalent interaction in the hydrogel, and the synergistic effect ofcovalent interaction and hydrogen bonding improves the mechanical properties of the hydrogel by nearly 10-fold. The hydrogel was observed to be able to withstand a stress of 368 Pa and to break in a layer-by-layer manner by compression testing. The micromechanics of the hydrogels were characterized, and the excellent mechanical properties of the hydrogels were confirmed. The synergistic approach provides a new idea for the preparation of low-molecular-weight peptide hydrogels and facilitates the expansion of their potential applications in biomedical fields.

Drosera-Inspired Dual-Actuating Double-Layer Hydrogel Actuator.

Drosera is a small insectivorous plant whose antennae can fold up, encircle, and prey. The rapid movement of the antennae is achieved by the synergistic effect of a double-layer structure with the antennae contracts on the front and expands on the back. In this work, a drosera-inspired dual-actuating double-layer hydrogel actuator is proposed, in which the temperature-responsive poly(N, N-diethyl acrylamide) (PDEAAm) layer acts as the main actuation layer and a moisture-responsive poly(acrylamide) (PAAm) layer acts as the auxiliary actuation layer. In a water environment with low temperature, both the PAAm and PDEAAm layers absorb water and expand with a swelling property. When the temperature exceeds the lower critical solution temperature of PDEAAm, the PDEAAm layer undergoes a hydrophilic-hydrophobic transition and shrinks rapidly. Therefore, the synergistic effect of the double-layer hydrogel enables the double-layer hydrogel to achieve a large bending angle at high temperature. In addition, when designing and fabricating shape-patterned double-layer hydrogels, complex shape changes can be achieved. Due to the physical and chemical properties, the actuator can be used to grab, transport, and release objects. This drosera-inspired double-layer hydrogel actuator has high practical value, which may provide new insights for the design and manufacture of artificial intelligence materials.

Single network double cross-linker (SNDCL) hydrogels with excellent stretchability, self-recovery, adhesion strength, and conductivity for human motion monitoring.

Hydrogels, as a kind of soft materials, are good candidates for smart skin-like materials. A double network is usually fabricated to improve the mechanical properties of hydrogels, and involves two different kinds of networks. In this work, a novel strategy for preparing single network double cross-linker (SNDCL) hydrogels was proposed and the prepared hydrogels exhibited excellent mechanical properties, including stretchability, compressibility, self-recovery, adhesion, shape memory and mechanical strength. N,N'-Methylenebisacrylamide forms covalent bonds with the network, while citric acid can form multiple weak interactions due to the polycarboxylic structure. This improves the tensile properties (6564%) and compressive properties of the hydrogel, and the hydrogels also exhibit long-lasting self-adhesion ability on various substrates. In addition, the hydrogels with multiple properties can be used as flexible strain sensors, allowing the monitoring of body movements. The hydrogels can hopefully be used in wearable electronic sensor devices and for healthcare monitoring.

Multiperformance PAM/PVA/CaCO3 Hydrogel for Flexible Sensing and Information Encryption.

Currently, the development of hydrogels with excellent mechanical properties (elasticity, fatigue resistance, etc.) and conductive properties can better meet their needs in the field of flexible sensor device applications. Generally, hydrogels with a denser cross-linking density tend to have better mechanical properties, but the improvement in mechanical properties comes at the expense of reduced electrical conductivity. Directly generating CaCO3 in the hydrogel prepolymer can not only increase the cross-linking density of its network but also introduce additional ions to enhance its internal ionic strength, which is beneficial to improving the conductivity of the hydrogel. It is still a big challenge to directly generate CaCO3 in the static prepolymer solution and ensure its uniform dispersion in the hydrogel. Herein, we adopted an improved preparation method to ensure that the directly generated CaCO3 particles can be evenly dispersed in the static prepolymer solution until the polymerization is completed. Finally, a PAM/PVA/CaCO3 hydrogel with supertensile, compressive, toughness, and fatigue resistance properties was prepared. In addition, the presence of free Na+ and Cl- gives the hydrogel excellent conductivity and sensing performance to monitor daily human activities. On the basis of the application of hydrogels in information communication, we have further deepened this application by combining the characteristics of hydrogels themselves. Combined with ASCII code, the hydrogel can also be applied in information exchange and information encryption and decryption, achieving the antitheft function in smart locks. A variety of excellent performance integrated PAM/PVA/CaCO3 hydrogels have broad application prospects for flexible sensors, highlighting great potential in human-computer interaction and intelligent information protection.

Straightforward oxidation of a copper substrate produces an underwater superoleophobic mesh for oil/water separation.

A superhydrophilic and underwater superoleophobic Cu(OH)2-covered mesh with micro- and nanoscale hierarchical composite structures is successfully fabricated through a one-step chemical oxidation of a smooth-copper mesh. Such mesh, without any further modification, can selectively separate water from oil/water mixtures with high separation efficiency, and possess excellent stability even after 60 uses. This method provides a simple, low-cost, and scalable strategy for the purification of oily wastewater.

Synthesis of functional poly(amidoamine) dendrimer decorated apple residue cellulose for efficient removal of aqueous Hg(II).

Water pollution caused by Hg(II) exerts hazardous effect to the environment and public health. The design and fabrication of eco-friendly bioadsorbents for efficient removal of Hg(II) from aqueous solution is a promising strategy. Herein, a series of bioadsorbents were synthesized by the decoration of apple residue cellulose with different generation (G) Schiff base functionalized poly(amidoamine) (PAMAM) dendrimers (SA-G0/CE, SA-G1.0/CE and SA-G2.0/CE). The structures of SA-G0/CE, SA-G1.0/CE and SA-G2.0/CE were characterized and their adsorption performances were determined comprehensively by considering various factors. The maximum adsorption capacity of SA-G0/CE, SA-G1.0/CE and SA-G2.0/CE for Hg(II) are 1.18, 1.73 and 1.88 mmol·g-1, respectively. The as-prepared bioadsorbents exhibit competitive adsorption capacity as compared with other reported adsorbents. Moreover, they exhibit remarkable adsorption selectivity toward Hg(II) with the coexistence of Ni(II), Cd(II), Mn(II), or Pb(II). The bioadsorbents display satisfactory adsorption performance in real water sample and can be reused with good regeneration property. Adsorption mechanism reveals that the functional groups of OH, -CONH-, CN and NC take part in the adsorption for Hg(II). The work not only opens a pathway to realize the reuse of apple residue, but also provides a promising strategy to construct efficient bioadsorbents for the decontamination of Hg(II) from aqueous solution.

Bionic ordered structured hydrogels: structure types, design strategies, optimization mechanism of mechanical properties and applications.

Natural organisms, such as lobsters, lotus, and humans, exhibit exceptional mechanical properties due to their ordered structures. However, traditional hydrogels have limitations in their mechanical and physical properties due to their disordered molecular structures when compared with natural organisms. Therefore, inspired by nature and the properties of hydrogels similar to those of biological soft tissues, researchers are increasingly focusing on how to investigate bionic ordered structured hydrogels and render them as bioengineering soft materials with unique mechanical properties. In this paper, we systematically introduce the various structure types, design strategies, and optimization mechanisms used to enhance the strength, toughness, and anti-fatigue properties of bionic ordered structured hydrogels in recent years. We further review the potential applications of bionic ordered structured hydrogels in various fields, including sensors, bioremediation materials, actuators, and impact-resistant materials. Finally, we summarize the challenges and future development prospects of bionic ordered structured hydrogels in preparation and applications.

Oxidized sodium alginate/polyacrylamide hydrogels adhesive for promoting wheat growth.

Chemical modification of sodium alginate (SA) polymer chains can increase its functional group species. Sodium periodate (SP) was usually used to oxidize the hydroxyl groups on the chain of SA to aldehyde groups, the preparation of oxidized sodium alginate (OSA) using SP is not only complicated, also limits the variety of functional groups on the chain of OSA. By contrast, we have developed an innovative strategy for OSA, in which ammonium persulfate (APS) was used to oxidize SA, providing a clear elucidation of the oxidizing process and mechanism. OSA/PAM hydrogels were synthesized using OSA, the hydrogels possess excellent adhesion properties to various non-metallic and metallic substrates. Tensile and compression tests show that the cross-linked OSA/PAM hydrogels have superior mechanical properties. We exploit OSA/PAM hydrogels as soil adhesive and water-retaining agents for wheat growth. OSA/PAM hydrogels significantly improve the survival time of wheat grown in brown loam soil under a water-shortage environment, and slow down the wilting of wheat in a water-shortage environment and prolong the survival time of wheat in sandy soils. Our trials should make hydrogels important for wheat cultivation in brown loam soils and the development of desert areas.

Reliable Manipulation of Gas Bubble Size on Superaerophilic Cones in Aqueous Media.

Gas bubbles in aqueous media are ubiquitous in a broad range of applications. In most cases, the size of the bubbles must be manipulated precisely. However, it is very difficult to control the size of gas bubbles. The size of gas bubbles is affected by many factors both during and after the generation process. Thus, precise manipulation of gas bubble size still remains a great challenge. The ratchet and conical hairs of the Chinese brush enable it to realize a significant capacity for holding ink and transferring them onto paper continuously and controllably. Inspired by this, a superhydrophobic/superaerophilic cone interface is developed to manipulate gas bubble size in aqueous media. When the resultant force between the Laplace force and the axial component of the buoyancy force approaches zero, the gas bubble is held steadily by the superhydrophobic/superaerophilic copper cones in a unique position (balance position). A new kind of pressure sensor is also designed based on this principle.

Spontaneous and Directional Bubble Transport on Porous Copper Wires with Complex Shapes in Aqueous Media.

Manipulation of gas bubble behaviors is crucial for gas bubble-related applications. Generally, the manipulation of gas bubble behaviors generally takes advantage of their buoyancy force. It is very difficult to control the transportation of gas bubbles in a specific direction. Several approaches have been developed to collect and transport bubbles in aqueous media; however, most reliable and effective manipulation of gas bubbles in aqueous media occurs on the interfaces with simple shapes (i.e., cylinder and cone shapes). Reliable strategies for spontaneous and directional transport of gas bubbles on interfaces with complex shapes remain enormously challenging. Herein, a type of 3D gradient porous network was constructed on copper wire interfaces, with rectangle, wave, and helix shapes. The superhydrophobic copper wires were immersed in water, and continuous and stable gas films then formed on the interfaces. With the assistance of the Laplace pressure gradient between two bubbles, gas bubbles (including microscopic gas bubbles) in the aqueous media were subsequently transported, continuously and directionally, on the copper wires with complex shapes. The small gas bubbles always moved to the larger ones.

RAFT-mediated Pickering emulsion polymerization with cellulose nanocrystals grafted with random copolymer as stabilizer.

The synthesis of a RAFT-mediated Pickering emulsion was firstly achieved by using cellulose nanocrystals (CNCs) grafted with a random copolymer as the stabilizer. Firstly, poly(acrylonitrile-r-butyl acrylate) (poly(AN-r-nBA)) was synthesized by Cu(0)-mediated CRP, which was further modified via a click chemistry strategy to obtain poly(ethylene tetrazole-r-butyl acrylate) (poly(VT-r-nBA)). Then, poly(VT-r-nBA) was grafted onto the CNCs through a Mitsunobu reaction to obtain poly(VT-r-nBA)-g-CNCs. Stabilized by poly(VT-r-nBA)-g-CNCs, an O/W RAFT-mediated Pickering emulsion was formed for the preparation of well-controlled poly(methyl methacrylate) (PMMA) particles with water-soluble potassium persulfate (KPS) as an initiator and oil-soluble 4-cyanopentanoic acid dithiobenzoate (CPADB) as a chain transfer agent. Rheological analysis suggested that the prepared Pickering emulsion possessed good stability under the influences of changes in strain, time, frequency and temperature. Furthermore, the recycling and further utilization of the poly(VT-r-nBA)-g-CNCs could be simply realized through centrifugal separation.

Dual-scaled porous nitrocellulose membranes with underwater superoleophobicity for highly efficient oil/water separation.

Large-area dual-scaled porous nitrocellulose (p-NC) membranes are fabricated by a facile, inexpensive and scalable perforating approach. These p-NC membranes show stable superhydrophilicity in air and underwater superoleophobicity. The p-NC membranes with intrinsic nanopores and array of microscale perforated pores could selectively and efficiently separate water from various oil/water mixtures with high efficiency (>99%) rapidly.

Structured cone arrays for continuous and effective collection of micron-sized oil droplets from water.

Environmental protection agencies and the petroleum industry require effective methods to separate micron-sized oil droplets from water. However, for most existing separation methods, phase separation occurs in the oil-water mixture. The remaining micron-scale oil droplets, which are not affected by phase separation, are difficult to handle with conventional methods on a large scale because of either a lack of separation ability or drawbacks in throughput capacity. Here we develop an oleophilic array of conical needle structures for the collection of micron-sized oil droplets, inspired by the collection of similar sized water droplets on conical cactus spines. Underwater, these structures mimic cacti and can capture micron-sized oil droplets and continuously transport them towards the base of the conical needles. Materials with this structure show obvious advantages in micron-sized oil collection with high continuity and high throughput.

Mussel-inspired chemistry and Michael addition reaction for efficient oil/water separation.

An oil/water separation mesh with high separation efficiency and intrusion pressure of water has been successfully developed by combining mussel-inspired chemistry and Michael addition reaction. The substrate of the stainless steel mesh was first coated with the adhesive polydopamine (PDA) film by simple immersion in an aqueous solution of dopamine at pH of 8.5. Then n-dodecyl mercaptan (NDM) was conjugated with PDA film through Michael addition reaction at ambient temperature. The as-prepared mesh showed highly hydrophobicity with the water contact angle of 144° and superoleophilicity with the oil contact angle of 0°. It can be used to separate a series of oil/water mixtures like gasoline, diesel, etc. The separation efficiency remains high after 30 times use (99.95% for hexane/water mixture). More importantly, the relatively high intrusion pressure (2.2 kPa) gives the opportunity to separation of large amount of oil and water mixtures. This study provides a new prospect to simply introduce multiple molecules on the adhesive PDA-based mesh to achieve various functional oil/water separation materials.

Underwater superoleophilicity to superoleophobicity: role of trapped air.

The interesting oil-wetting behavior to a superamphiphobic surface in water has been investigated. We demonstrated that the trapped air can tune the underwater wettability of the surface, changing from superoleophilic to superoleophobic. The trapped air in the grooves of the superamphiphobic surface can cause the significant change of the three-phase contact line (TCL).

Clam's shell inspired high-energy inorganic coatings with underwater low adhesive superoleophobicity.

Unique underwater low adhesive superoleophobicity is discovered on the pallium-covered region of a short clam's shell. This property originates from the shell's inorganic composition of CaCO(3) and surface micro/nano-hierarchical structures. The oil-repellent shell provides an innovative strategy to develop novel underwater superoleophobic coatings using inorganic oxides such as copper oxide. This kind of coating is anticipated to be applied on engineering metals to protect aquatic equipment from oil contamination.

Bioinspired oil strider floating at the oil/water interface supported by huge superoleophobic force.

Oil pollution to aquatic devices, especially to those oil-cleaning devices and equipment-repairing robots during oil spill accidents, has drawn great attention and remains an urgent problem to be resolved. Developing devices that can move freely in an oil/water system without contamination from oil has both scientific and practical importance. In nature, the insect water strider can float on water by utilizing the superhydrophobic supporting force received by its legs. Inspired by this unique floating phenomenon, in this article, we designed a model device named "oil strider" that could float stably at the oil/water interface without contamination by oil. The floating capability of the oil strider originated from the huge underwater superoleophobic supporting force its "legs" received. We prepared the micro/nanohierarchical structured copper-oxide-coated copper wires, acting as the artificial legs of oil strider, by a simple base-corrosion process. The surface structures and hydrophilic chemical components of the coatings on copper wires induced the huge superoleophobic force at the oil/water interface, to support the oil strider from sinking into the oil. Experimental results and theoretical analysis demonstrate that this supporting force is mainly composed of three parts: the buoyancy force, the curvature force, and the deformation force. We anticipate that this artificial oil strider will provide a guide for the design of smart aquatic devices that can move freely in an oil/water system with excellent oil repellent capability, and be helpful in practical situations such as oil handling and oil spill cleanup.