A win-win scenario for antibacterial activity and skin mildness of cationic surfactants based on the modulation of host-guest supramolecular conformation.

The commercial cationic surfactants (CSAa) with quaternary ammonium (QA) groups have proved to be broad-spectrum bactericide against bacteria, fungi, and viruses. Nevertheless, they inevitably exhibit potent irritation on the skin. In this work, we systematically investigated the regulatory mechanism of the host-guest supramolecular conformation with ß-cyclodextrin (ß-CD) on the bactericidal performance and skin irritation of CSAa with different head groups and chain lengths. When the ratio of incorporated ß-CD is not greater than 1:1, the bactericidal efficiency of CSAa@ß-CD (n > 12) remained above 90 % due to the free QA groups and hydrophobic fraction that can act on negatively charged bacterial membranes. And once the ratio of ß-CD exceeded 1:1, the ß-CD attracted to the bacterial surface by hydrogen bonding might prevent CSAa@ß-CD from acting on bacteria, resulting in a decrement in antibacterial performance. Even so, the antibacterial activity of CSAa with long alkyl chains (n = 16, 18) was independent from the complexation of ß-CD. Accordingly, both the zein solubilization assay and the neutrophil migration assay on zebrafish skin evidenced that ß-CD attenuated the interaction of surfactant with skin model proteins and the inflammatory effect on zebrafish, thereby enhancing skin mildness. In this way, we hope to create a simple but effective brainpower using the host-guest approach to guarantee both bactericidal efficiency and skin mildness without modifying the chemical structure of these commercial biocides.

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.

Physical Insight into the Conditions Required in the Solid-Phase Molecular Self-Assembly of SDS Revealed by Coarse-Grained Molecular Dynamics Simulation.

Molecular self-assembled materials have attracted considerable interest in recent years. As part of the efforts to overcome the shortcoming that the solution-based methods were hardly applicable in preparing bulk macroscopic molecular self-assemblies, Yan [ CCS Chem. 2020, 2, 98-106] developed a strategy of solid-phase molecular self-assembly (SPMSA) that allows scaling up the generation of massive supramolecular films. It is highly desired to understand the physical insight into the SPMSA at a molecular level. Here, in combination with the experimental study, we report molecular dynamics (MD) simulations on the SPMSA of the surfactant sodium dodecyl sulfate (SDS) using a coarse-grained method with the Martini force field model. The MD simulations clearly manifest that a small amount of water is required to endow the SDS molecules with sufficient mobility to self-assemble, and the smaller size of the preassembled SDS particles favors their further fusion into mesophases by reducing the total surface Gibbs free energy, while the smaller interparticle distance decreases the time for the particle fusion. The simulation results agree well with the conditions required in the experiment, confirming that SMPSA is a free-energy-favored process leading to bulk self-assembled materials.

Enzyme-Responsive Aqueous Two-Phase Systems in a Cationic-Anionic Surfactant Mixture.

Enzyme-instructed self-assembly is an increasingly attractive topic owing to its broad applications in biomaterials and biomedicine. In this work, we report an approach to construct enzyme-responsive aqueous surfactant two-phase (ASTP) systems serving as enzyme substrates by using a cationic surfactant (myristoylcholine chloride) and a series of anionic surfactants. Driven by the hydrophobic interaction and electrostatic attraction, self-assemblies of cationic-anionic surfactant mixtures result in biphasic systems containing condensed lamellar structures and coexisting dilute solutions, which turn into homogeneous aqueous phases in the presence of hydrolase (cholinesterase). The enzyme-sensitive ASTP systems reported in this work highlight potential applications in the active control of biomolecular enrichment/release and visual detection of cholinesterase.

Generating circularly polarized luminescence from clusterization-triggered emission using solid phase molecular self-assembly.

Purely-organic clusterization-triggered emission (CTE) has displayed promising abilities in bioimaging, chemical sensing, and multicolor luminescence. However, it remains absent in the field of circularly polarized luminescence (CPL) due to the difficulties in well-aligning the nonconventional luminogens. We report a case of CPL generated with CTE using the solid phase molecular self-assembly (SPMSA) of poly-L-lysine (PLL) and oleate ion (OL), that is, the macroscopic CPL supramolecular film self-assembled by the electrostatic complex of PLL/OL under mechanical pressure. Well-defined interface charge distribution, given by lamellar mesophases of OL ions, forces the PLL chains to fold regularly as a requirement of optimal electrostatic interactions. Further facilitated by hydrogen bonding, the through-space conjugation (TSC) of orderly aligned electron-rich O and N atoms leads to CTE-based CPL, which is capable of transferring energy to an acceptor via a Förster resonance energy transfer (FRET) process, making it possible to develop environmentally friendly and economic CPL from sustainable and renewable materials.

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.

Putting Ink into Polyion Micelles: Full-Color Anticounterfeiting with Water/Organic Solvent Dual Resistance.

Anticounterfeiting paintings are usually with limited colors and easy blurring and need to be dispersed in an environmentally unfriendly organic solvent. We report a set of water-based polyion micellar inks to solve all these problems. Upon complexation of reversible coordination polymers formed with rare earth metal ions Eu3+ and Tb3+ and the aggregation-induced emission ligand tetraphenylethylene-L2EO4 with oppositely charged block polyelectrolyte P2MVP29-b-PEO205, we are able to generate polyion micelles displaying three elementary emission colors of red (R) (ΦEu3+ = 24%), green (G) (ΦTb3+ = 7%), and blue (B) (ΦTPE = 9%). Full-spectrum emission and white light emission (0.34, 0.34) become possible by simply mixing the R, G, and B micelles at the desired fraction. Strikingly, the micellar inks remain stable even after soaking in water or organic solvents (ethyl acetate, ethanol, etc.) for 24 h. We envision that polyion micelles would open a new paradigm in the field of anticounterfeiting.

Self-Assembly of Aggregation-Induced-Emission Molecules.

The last decade has witnessed rapid developments in aggregation-induced emission (AIE). In contrast to traditional aggregation, which causes luminescence quenching (ACQ), AIE is a reverse phenomenon that allows robust luminescence to be retained in aggregated and solid states. This makes it possible to fabricate various highly efficient luminescent materials, which opens new paradigms in a number of fields, such as imaging, sensing, medical therapy, light harvesting, light-emitting devices, and organic electronic devices. Of the various important features of AIE molecules, their self-assembly behavior is very attractive because the formation of a well-defined emissive nanostructure may lead to advanced applications in diverse fields. However, due to the nonplanar topology of AIEgens, it is not easy for them to self-assemble into well-defined structures. To date, some strategies have been proposed to achieve the self-assembly of AIEgens. Herein, we summarize the most recent approaches for the self-assembly of AIE molecules. These approaches can be sorted into two classes: 1) covalent molecular design and 2) noncovalent supramolecular interactions. We hope this will inspire more excellent work in the field of AIE.

An efficient solvent additive for the preparation of anion-cation-mixed hybrid and the high performance perovskite solar cells.

Lead amine halide perovskite solar cells have been dominating photovoltaic research in this decade. The quality of the perovskite layer plays a significant role in the photovoltaic performance of planar perovskite devices, and solvent engineering is an effective method to improve the quality of the perovskite layer. Here, we introduce acetonitrile (ACN) as an effective solvent additive in the preparation of cation-anion-mixed perovskite of Cs0.05(MA0.17FA0.83)0.95Pb(I0.83Br0.17)3. The morphology observation indicates that a large grain, compact and pinhole-free perovskite layer is obtained by ACN adding. Steady-state and time-resolved photoluminescence measurements demonstrate fewer defects and less carrier recombination in the perovskite layer with ACN adding. The planar perovskite solar cell with ACN adding achieves a power conversion efficiency of 19.15% with slight hysteresis and stable output, while the device without ACN adding gets an efficiency of 17.47% under the same experiment conditions. The simple and green preparation process and the significant improvement of the device performance render this method promising.

Allosteric Self-Assembly of Coordinating Terthiophene Amphiphile for Triggered Light Harvesting.

Allosteric regulation is extensively employed by nature to achieve functional control of protein or deoxyribonucleic acid through triggered conformational change at a remote site. We report that a similar strategy can be utilized in artificial self-assembly to control the self-assembled structure and its function. We show that on binding of metal ions to the headgroup of an amphiphile TTC4L, the conformational change may lead to change of the dipole orientation of the energy donor at the chain end. This on the one hand leads to a drastically different self-assembled structure; on the other hand, it enables light harvesting between the donor-acceptor. Because the Forster resonance fluorescence transfer efficiency is gated by metal ions, controlling the feeding of metal ions allows switching on and off of light harvesting. We expect that using allosteric self-assembly, we will be able to create abundant structures with distinct function from limited molecules, which show prominent potential for the postorganic modification of the structure and function of self-assembled materials.

Self-assembly facilitated and visible light-driven generation of carbon dots.

Carbon dots (CDs) with an absolute fluorescence quantum yield of 87% are facilely prepared via irradiation of self-assembled terthiophene amphiphile TTC4L in aqueous solution by mild visible light. Visible light irradiation of TTC4L triggers the production of superoxide radicals in water, which oxidize the closely packed terthiophene group into carbon dots. Our results reveal that the molecular self-assembly may act as important precursor for the generation of single molecule-like carbon dots; this method paves the way for the fabrication of CDs of high quality.