Dynamic covalent surfactants and their uses in the development of smart materials.

Dynamic covalent chemistry, which leverages the dynamic nature of reversible covalent bonds controlled by the conditions of reaction equilibrium, has demonstrated great potential in diverse applications related to both the stability of covalent bonds and the possibility of exchanging building blocks, imparting to the systems the possibility of "error checking" and "proof-reading". By incorporating dynamic covalent bonds into surfactant molecular architectures, combinatorial libraries of surfactants with bespoke functionalities can be readily fabricated through a facile strategy, with minimum effort in organic synthesis. Consequently, a multidisciplinary field of research involving the creation and application of dynamic covalent surfactants has recently emerged, which has aroused great attention in surfactant and colloid science, supramolecular chemistry, self-assembly, smart materials, drug delivery, and nanotechnology. This review reports results in this field published over recent years, discusses the possibilities presented by dynamic covalent surfactants and their applications in developing smart self-assembled materials, and outlines some future perspectives.

Relaxing Wrinkles in Jammed Interfacial Assemblies.

Dynamic covalent bonding has emerged as a mean by which stresses in a network can be relaxed. Here, the strength of the bonding of ligands to nanoparticles at the interface between two immiscible liquids affect the same results in jammed assemblies of nanoparticle surfactants. Beyond a critical degree of overcrowding induced by the compression of jammed interfacial assemblies, the bonding of ligands to nanoparticles (NPs) can be broken, resulting in a desorption of the NPs from the interface. This reduces the areal density of nanoparticle surfactants at the interface, allowing the assemblies to relax, not to a fluid state but rather another jammed state. The relaxation of the wrinkles caused by the compression reflects the tendency of these assemblies to eliminate areas of high curvature, favoring a more planar geometry. This enabled the generation of giant vesicular and multivesicular structures from these assemblies.

Mechanosensitive non-equilibrium supramolecular polymerization in closed chemical systems.

Chemical fuel-driven supramolecular systems have been developed showing out-of-equilibrium functions such as transient gelation and oscillations. However, these systems suffer from undesired waste accumulation and they function only in open systems. Herein, we report non-equilibrium supramolecular polymerizations in a closed system, which is built by viologens and pyranine in the presence of hydrazine hydrate. On shaking, the viologens are quickly oxidated by air followed by self-assembly of pyranine into micrometer-sized nanotubes. The self-assembled nanotubes disassemble spontaneously over time by the reduced agent, with nitrogen as the only waste product. Our mechanosensitive dissipative system can be extended to fabricate a chiral transient supramolecular helix by introducing chiral-charged small molecules. Moreover, we show that shaking induces transient fluorescence enhancement or quenching depending on substitution of viologens. Ultrasound is introduced as a specific shaking way to generate template-free reproducible patterns. Additionally, the shake-driven transient polymerization of amphiphilic naphthalenetetracarboxylic diimide serves as further evidence of the versatility of our mechanosensitive non-equilibrium system.

A versatile and tunable bio-patterning platform for the construction of various cell array biochips.

In this work, we report a versatile and tunable platform for the construction of various cell array biochips using a simple soft lithographic approach to pattern polydopamine (PDA) arrays via microcontact printing (µCP). Instead of direct polymerization of PDA on the polydimethylsiloxane (PDMS) tips, dopamine monomers were first printed on the substrate followed by a self-oxidative polymerization step facilitated by ammonia vapor to grow PDA in situ, which greatly reduced the reaction time and prevented the PDMS tips from damaging. The improved robustness and utility of the PDMS tips allows the formation of tunable PDA array chips with controllable PDA feature size and shape. As a result, single cell, multi-cells and cell line arrays can be constructed. The obtained cell array chips showed high single cell capture efficiency, providing a standardized single cell array analysis platform. Meanwhile, the adhered cells can maintain excellent viability and proliferation ability on the PDA chips. Moreover, a cytotoxicity sensor with single cell resolution was enabled on the single cell array chip. This work provides a promising cell array biochip platform for high-throughput cellular analysis and cell screening.

A Gemini-Type Superwettable Separator for Consecutive Purification of Water and Oil Phases from Oil-Water Mixtures and Emulsions.

Oil pollution results from daily activities and a variety of industries have caused not only severe environmental problems but also wastage of valuable petrochemical resources. Separation based on superwettable materials holds promise; however, practical applications of a single type of superwettable materials were often limited due to their ability in treatment of complicated oil-water systems. Herein, a Gemini-type separator was created through the cooperation of two kinds of superwettable sand particles with opposite wettability, i. e., one is superhydrophobic whereas the other is superhydrophilic. Cooperatively by the two types of superwettable sand, consecutive separation and purification of both water and oil phases from complicated oil-water systems (e. g., water mixed with a lighter or denser oil, water emulsified in oil, oil emulsified in water, and/or a combination of them in one batch) could be achieved with high flux and superior efficiency just in one single operation unit.

Sand-Based Economical Micro/Nanocomposite Materials for Diverse Applications.

Sand is one of the most fundamental construction materials that is of significant importance and widely used for making concrete, plasters, and mortars, and also for filling under floor and basements. Sand-derived functional materials, for instance superhydrophobic sand, which can be used to prepare liquid marble, separate oil-water mixtures, and transport liquids, have recently been a highly topical and promising research field. However, such materials are mainly prepared using valuable surface modification agents via complicated procedures that are difficult for mass-production, which restricted their true applications. Here, we developed a simple, low-cost, and efficient method for the development of sand-based hierarchical micro/nanostructured composite materials with diverse applications. Briefly, micro/nanostructured superhydrophobic sand was synthesized by one-step in situ growth of a network layer of silicone nanofilaments on the surface of sand microparticles, using only one cheap chemical of small molecules of silanes. The as-prepared superhydrophobic sand displays excellent performance in waterproofing, water storage, soil moisturizing, and oil-water separation. Furthermore, sand-supported micro/nanocomposite catalysts were obtained through covalent attachment of polyamines on the surface of silicone nanofilaments. Such composites, packed in a glass column, were used as a simple flow reactor for Knoevenagel condensation reactions. Quantitative amounts of pure products without further purification can be obtained in such a simple way that just allowing the reactants solution flows through the composite catalysts driven by gravity. These results pave the way toward the development of sand-based multifunctional materials with great potential for industrial use, given their versatile functions and excellent performances but easy-to-fabricate, low-cost preparation procedure.

Fast-Charging Nonaqueous Potassium-Ion Batteries Enabled by Rational Construction of Oxygen-Rich Porous Nanofiber Anodes.

Practical applications of carbon anodes in high-power potassium-ion batteries (PIBs) were hampered by their limited rate properties, due to the sluggish K+ transport kinetics in the bulk. Constructing convenient ion/electron transfer channels in the electrode is of great importance to realize fast charge/discharge rates. Here, cross-linked porous carbon nanofibers (inner porous carbon nanotubes and outer soft carbon layer) modified with oxygen-containing functional groups were well designed as anodes to realize robust de-/potassiation kinetics. The novel anode delivered excellent rate capabilities (107 mAh g-1 at 20 A g-1 and 78 mAh g-1 at 40 A g-1) and superior cycling stability (76% capacity retention after 14,000 cycles at 2 A g-1). In situ XRD measurement, in situ Raman spectra, and galvanostatic intermittent titration verified its surface-dominated potassium storage behavior with fast de-/potassiation kinetics, excellent reversibility, and rapid ion/electron transport. Moreover, theoretical investigation revealed that the carboxyl groups in the carbon offered additional capacitive adsorption sites for K+, thus significantly enhancing the reversible capacity. Surprisingly, a full cell using the anode and perylene-3,4,9,10-tetracarboxylic dianhydride cathode achieved an outstanding power density of 23,750 W kg-1 and superior fast charge/slow discharge performance.

Electrostatic co-assembly of nanoparticles with oppositely charged small molecules into static and dynamic superstructures.

Coulombic interactions can be used to assemble charged nanoparticles into higher-order structures, but the process requires oppositely charged partners that are similarly sized. The ability to mediate the assembly of such charged nanoparticles using structurally simple small molecules would greatly facilitate the fabrication of nanostructured materials and harnessing their applications in catalysis, sensing and photonics. Here we show that small molecules with as few as three electric charges can effectively induce attractive interactions between oppositely charged nanoparticles in water. These interactions can guide the assembly of charged nanoparticles into colloidal crystals of a quality previously only thought to result from their co-crystallization with oppositely charged nanoparticles of a similar size. Transient nanoparticle assemblies can be generated using positively charged nanoparticles and multiply charged anions that are enzymatically hydrolysed into mono- and/or dianions. Our findings demonstrate an approach for the facile fabrication, manipulation and further investigation of static and dynamic nanostructured materials in aqueous environments.

The Many Ways to Assemble Nanoparticles Using Light.

The ability to reversibly assemble nanoparticles using light is both fundamentally interesting and important for applications ranging from reversible data storage to controlled drug delivery. Here, the diverse approaches that have so far been developed to control the self-assembly of nanoparticles using light are reviewed and compared. These approaches include functionalizing nanoparticles with monolayers of photoresponsive molecules, placing them in photoresponsive media capable of reversibly protonating the particles under light, and decorating plasmonic nanoparticles with thermoresponsive polymers, to name just a few. The applicability of these methods to larger, micrometer-sized particles is also discussed. Finally, several perspectives on further developments in the field are offered.

Polysilsesquioxane Nanowire Networks as an "Artificial Solvent" for Reversible Operation of Photochromic Molecules.

Efficient isomerization of photochromic molecules often requires conformational freedom and is typically not available under solvent-free conditions. Here, we report a general methodology allowing for reversible switching of such molecules on the surfaces of solid materials. Our method is based on dispersing photochromic compounds within polysilsesquioxane nanowire networks (PNNs), which can be fabricated as transparent, highly porous, micrometer-thick layers on various substrates. We found that azobenzene switching within the PNNs proceeded unusually fast compared with the same molecules in liquid solvents. Efficient isomerization of another photochromic system, spiropyran, from a colorless to a colored form was used to create reversible images in PNN-coated glass. The coloration reaction could be induced with sunlight and is of interest for developing "smart" windows.

Effect of residual chemicals on wormlike micelles assembled from a C22-tailed cationic surfactant.

HYPOTHESIS: Ultra-long-chain surfactants, particularly C22-tailed ones, have attracted considerable attention because of their ease of self-assembly into wormlike micelles (WLMs). Commercial C22-tailed surfactants often contain non-negligible amounts of chemical residues introduced during their production. Since the noncovalent driving force of wormlike self-assembly can be greatly affected by the composition, we hypothesized that the residual chemicals could play a significant role in tuning the micelle microstructure and macroscopic properties of the surfactants. EXPERIMENTS: To confirm this hypothesis, a highly pure (>99%) C22-tailed cationic surfactant, N-erucylamidopropyl-N,N,N-trimethylammonium iodide (EDAI) was synthesized, and various amounts of corresponding reactants (iodomethane or N-erucamidopropyl-N,N-dimethylamine) or solvents (acetone) commonly used in surfactant synthesis were introduced as residues. The impact of each individual residue on the macroscopic appearances, rheological properties, and micelle morphology of the surfactant solution were investigated. FINDINGS: Increasing the residue fraction in the EDAI solution resulted in an initial increase, followed by a dramatic drop in solution viscosity. This behavior was described in terms of micellar structural transformations based on analysis of cryo-TEM observations and surface tension measurements. These findings are of crucial importance in understanding the sophisticated behaviors of WLMs and will benefit the industrial preparation of ultra-long-chain surfactants for commercial use.

Supramolecular Control of Azobenzene Switching on Nanoparticles.

The reversible photoisomerization of azobenzene has been utilized to construct a plethora of systems in which optical, electronic, catalytic, and other properties can be controlled by light. However, owing to azobenzene's hydrophobic nature, most of these examples have been realized only in organic solvents, and systems operating in water are relatively scarce. Here, we show that by coadsorbing the inherently hydrophobic azobenzenes with water-solubilizing ligands on the same nanoparticulate platforms, it is possible to render them essentially water-soluble. To this end, we developed a modified nanoparticle functionalization procedure allowing us to precisely fine-tune the amount of azobenzene on the functionalized nanoparticles. Molecular dynamics simulations helped us to identify two distinct supramolecular architectures (depending on the length of the background ligand) on these nanoparticles, which can explain their excellent aqueous solubilities. Azobenzenes adsorbed on these water-soluble nanoparticles exhibit highly reversible photoisomerization upon exposure to UV and visible light. Importantly, the mixed-monolayer approach allowed us to systematically investigate how the background ligand affects the switching properties of azobenzene. We found that the nature of the background ligand has a profound effect on the kinetics of azobenzene switching. For example, a hydroxy-terminated background ligand is capable of accelerating the back-isomerization reaction by more than 6000-fold. These results pave the way toward the development of novel light-responsive nanomaterials operating in aqueous media and, in the long run, in biological environments.

Reversible photoswitching of encapsulated azobenzenes in water.

Efficient molecular switching in confined spaces is critical for the successful development of artificial molecular machines. However, molecular switching events often entail large structural changes and therefore require conformational freedom, which is typically limited under confinement conditions. Here, we investigated the behavior of azobenzene-the key building block of light-controlled molecular machines-in a confined environment that is flexible and can adapt its shape to that of the bound guest. To this end, we encapsulated several structurally diverse azobenzenes within the cavity of a flexible, water-soluble coordination cage, and investigated their light-responsive behavior. Using UV/Vis absorption spectroscopy and a combination of NMR methods, we showed that each of the encapsulated azobenzenes exhibited distinct switching properties. An azobenzene forming a 1:1 host-guest inclusion complex could be efficiently photoisomerized in a reversible fashion. In contrast, successful switching in inclusion complexes incorporating two azobenzene guests was dependent on the availability of free cages in the system, and it involved reversible trafficking of azobenzene between the cages. In the absence of extra cages, photoswitching was either suppressed or it involved expulsion of azobenzene from the cage and consequently its precipitation from the solution. This finding was utilized to develop an information storage medium in which messages could be written and erased in a reversible fashion using light.

"Precipitation on Nanoparticles": Attractive Intermolecular Interactions Stabilize Specific Ligand Ratios on the Surfaces of Nanoparticles.

Confining organic molecules to the surfaces of inorganic nanoparticles can induce intermolecular interactions between them, which can affect the composition of the mixed self-assembled monolayers obtained by co-adsorption from solution of two different molecules. Two thiolated ligands (a dialkylviologen and a zwitterionic sulfobetaine) that can interact with each other electrostatically were coadsorbed onto gold nanoparticles. The nanoparticles favor a narrow range of ratios of these two molecules that is largely independent of the molar ratio in solution. Changing the solution molar ratio of the two ligands by a factor of 5 000 affects the on-nanoparticle ratio of these ligands by only threefold. This behavior is reminiscent of the formation of insoluble inorganic salts (such as AgCl), which similarly compensate positive and negative charges upon crystallizing. Our results pave the way towards developing well-defined hybrid organic-inorganic nanostructures.

Multifunctional Hybrid Porous Micro-/Nanocomposite Materials.

Multifunctional hybrid porous micro-/nanocomposite materials with hierarchical structures of soft silicone nanofilaments on hard porous glass microbeads are designed and synthesized. Such materials display selective super-antiwetting/superwetting properties with unique mechanical, chemical, and thermal stabilities, as well as excellent antifouling properties. They are ideal materials for highly efficient separation of oil/water mixtures and emulsions, and display great advantages as carriers for organocatalysts.

pH-Tunable wormlike micelles based on an ultra-long-chain "pseudo" gemini surfactant.

Smart surfactant wormlike micelles (SWLMs), responsive to external stimuli, are a particularly recent area of development, yet highly promising, given the versatility of the materials but simplicity of the design. Here, we developed a pH-switchable wormlike micellar system based on a "pseudo" gemini surfactant (named as EAMA) formed by a mixture of N-erucamido-N,N-dimethylamine (UC22AMPM) and maleic acid with a molar ratio of 2 : 1, and compared the "pseudo" gemini worm system with UC22AMPM in the presence of hydrochloric acid (EAHCl). It was found that both maleic acid and hydrochloric acid can protonate the ultra-long-chain tertiary amine into a quaternary ammonium surfactant, thereby forming wormlike micelles; however, much stronger viscoelastic behavior was evidenced in the maleic acid system because one protonated maleic acid molecule can "bridge" two quaternized UC22AMPM molecules via electrostatic attraction. In contrast, the EAHCl system just shows a "mono" quaternary ammonium feature with a weak viscosity buildup. In addition, the maleic acid-based worm system was found to be more thermo-sensitive than conventional wormlike micelles, which also originates due to its "pseudo" gemini architecture.

Versatile method for AFM-tip functionalization with biomolecules: fishing a ligand by means of an in situ click reaction.

A facile and universal method for the functionalization of an AFM tip has been developed for chemical force spectroscopy (CFS) studies of intermolecular interactions of biomolecules. A click reaction between tripod-acetylene and an azide-linker-ligand molecule was successfully carried out on the AFM tip surface and used for the CFS study of ligand-receptor interactions.

Oil/water separation with selective superantiwetting/superwetting surface materials.

The separation of oil from oily water is an important pursuit because of increasing worldwide oil pollution. Separation by the use of materials with selective oil/water absorption is a relatively recent area of development, yet highly promising. Owing to their selective superantiwetting/superwetting properties towards water and oil, superhydrophobic/superoleophilic surfaces and underwater superoleophobic surfaces have been developed for the separation of oil/water-free mixtures and emulsions. In this Review, after a short introduction to oil/water separation, we describe the principles of materials with selective oil/water absorption and outline recent advances in oil/water separation with superwetting/superantiwetting materials, including their design, their fabrication, and models of experimental setups. Finally, we discuss the current state of this new field and point out the remaining problems and future challenges.

Superamphiphobic surfaces.

Superamphiphobicity is an effect where surface roughness and surface chemistry combine to generate surfaces which are both superhydrophobic and superoleophobic, i.e., contact angles (θCA) greater than 150° along with low contact angle hysteresis (CAH) not only towards probing water but also for low-surface-tension 'oils'. In this review, we summarize the research on superamphiphobic surfaces, including the characterization of superamphiphobicity, different techniques towards the fabrication of surface roughness and surface modification with low-surface-energy materials as well as their functional applications.