Solid-Phase Molecular Self-Assembly Enabled Glue-Free Antifatigue Laminate Programmable Materials.

Repeated programmability has emerged as a desired property in smart device engineering, but the programmability will fatigue upon repeated applications due to the unmatched mechanical property between the layer materials and the polymeric glue that is required to integrate the two individual oriented layers. It is reported here that glue-free antifatigue programmable laminate materials can be made with films resulted from solid-phase molecular self-assembly (SPMSA). The SPMSA films are created by squeezing the precipitates of oppositely charged polyelectrolytes and DTAB with a noodle machine, where the hydrophobic DTAB molecules self-assembled into wormlike micelles and oriented along the squeezing direction. The surface molecules in this film are endowed with sufficient mobility in the presence of hydration water, so that two such films are able to be pressed into a laminate material owing to the hydrophobic and electrostatic interactions between the molecules on the two adjacent surfaces. As the water evaporated gradually, the left laminate materials are glue-free with the same composition. When many of such films are integrated with specific designs, complicated shape programming is able to be achieved, and the programmability is reversible without fatigue. The current strategy is envisioned as a potent intriguing pathway leading to advanced programable materials.

Effect of the Molecular Weight of Polyelectrolyte and Surfactant Chain Length on the Solid-Phase Molecular Self-Assembly.

Solid-phase molecular self-assembly (SPMSA) is emerging as an efficient approach, leading to scale-span self-assembled supramolecular films. With SPMSA, freestanding macroscopic supramolecular films can be formed upon mechanically pressing the precipitates formed with polyelectrolytes and oppositely charged surfactants. Herein, we report that the film formation ability and the mechanical strength of the resultant film depend highly on the surfactant chain lengths and the molecular weight of polyelectrolytes. A coarse-grained molecular dynamics study revealed that the longer surfactant chains are beneficial for the ordered assembly of surfactant bilayers in the film, whereas the larger molecular weight of PE favors the enhanced mechanical strength of the film by promoting the long-range order of the surfactant bilayers. The current results disclosed the physical insight of the surfactant chain length and the molecular weight of polyelectrolytes into the film structure and mechanical strength, which is of practical importance in guiding the creation of SPMSA materials.

Unprecedented Nonflammable Organic Adhesives Leading to Fireproof Wood Products.

We report an excellent water-based inflammable organic wood adhesive that is able to protect wood products from burning by generating inflammable gases, a porous thick char layer, and radicals that consume the oxygen and hydrogen radicals required in the burning process. The organic adhesive is obtained by the formation of hard supramolecular phases composed of high-density flame-retardant N and P elements through hydrogen bonding and acid-base interaction between the phytic acid and branched polyethylenimine (b-PEI). The phytic acid molecules are packed densely in the framework of the flexible b-PEI so that a porous char layer that would reduce heat conduction can be formed as the adhesive is heated. Together with the formation of inflammable NH3 gas to dilute the oxygen concentration and a PO• radical to capture the H• and O• radicals, the adhesive-treated wood product displays an extremely high limited oxygen index of 100% and a negligible heat release rate, total heat release, and total smoke release. The current flame-retardant water-based organic adhesive is so far the best adhesive for green and safe wood products from burning.

Wearable Sensors Based on Solid-Phase Molecular Self-Assembly: Moisture-Strain Dual Responsiveness Facilitated Extremely High and Damage-Resistant Sensitivity.

Wearable sensing technologies have gained increasing interest in biomedical fields because they are convenient and could efficiently monitor health conditions by detecting various physiological signals in real time. However, common film sensors often neglect body moisture and enhance the sensitivity by enhancing the conductive dopants and self-healing ability. We report in this work a supramolecular film sensor based on solid-phase molecular self-assembly (SPMSA), which smartly utilizes the body moisture to enhance the sensitivity for human-machine interaction. The carbon nanotube (CNT)-doped SPMSA film is able to capture environmental moisture quickly. Upon contact to human skin, the moisture not only promotes the junction between CNTs but also contributes to the conductivity. As a result, the sensitivity can be enhanced 4 times. In this way, we are able to obtain the highest sensitivity of 700% with the lowest CNT doping rate of 0.5%. Furthermore, the current sensor displays damage-inert sensing performance. In the presence of a hole of up to 50% of the film area, the sensitivity remains unaffected due to the decreases in the absolute conductivity of the film sensor before and after a trigger to the same extent. In this way, we have developed a new principle in the design of a film sensor for human-machine interaction, which releases the sensor from focus on promoting conductivity and self-healing materials.

Folic Acid-Based Coacervate Leading to a Double-Sided Tape for Adhesion of Diverse Wet and Dry Substrates.

Adhesives are crucial both in nature and in diversified artificial fields, and developing environment-friendly adhesives with economic procedures remains a great challenge. We report that folic acid-based coacervates can be a new category of excellent adhesives for all kinds of surfaces with long-lasting adhesiveness. Aided by the electrostatic interaction between the π-π stacked folic acid quartets and polycations, the resultant coacervates are able to interact with diversified substrates via a polyvalent hydrogen bond, coordination, and electrostatic interactions. The adhesivity to wood is superior to the strong commercial glues, but without releasing any toxic components. Upon evaporating water, the coacervate can be casted into a non-adhesive flexible self-supporting film, which restores the adhesive coacervate immediately on contacting water with original adhesive ability. In this way, the coacervate can be facilely tailored into a double-sided tape (DST), which is convenient for storage and application under ambient conditions. Given its excellent adhesive performance, release of nontoxic gases, and convenience in storage and application, the folic acid-based DST is very promising as a new adhesive material.

Green Wood Adhesives from One-Pot Coacervation of Folic Acid and Branched Poly(ethylene imine).

Adhesives are extensively used in furniture manufacture, and most currently utilized furniture glues are formaldehyde-based chemicals, which emit formaldehyde throughout the entire life of the furniture. With increasing concerns about formaldehyde emission effects on human health, formaldehyde-free and environmentally friendly wood adhesives from bio-based resources are highly desired. In this study, we developed an eco-friendly, high-strength, and water-based wood adhesive from one-pot coacervation of the hierarchical self-assembly of folic acid (FA, a biomolecule, vitamin B9) with a commercially available biocompatible polymer-branched poly(ethylene imine) (b-PEI). The coacervation is caused by multiple hydrogen bonds between b-PEI and the stacks of FA quartets, which demonstrates a continuous robust 3D network, thus realizing adhesion and cohesion behaviors. This coacervate has the strongest adhesion toward wood compared with other substrates. The long-lasting shear bonding strength is up to 3.68 MPa, which is much higher than that of commercial super glue, but without releasing any toxic components. Since all the fabrication and application processes are under ambient conditions without any heating and high-pressure procedures, this work provides a facile yet powerful strategy to develop formaldehyde-free, eco-friendly, and high-performance bio-based waterborne adhesives for wood bonding.