'Rewritable' and 'liquid-specific' recognizable wettability pattern.

Bio-inspired surfaces with wettability patterns display a unique ability for liquid manipulations. Sacrificing anti-wetting property for confining liquids irrespective of their surface tension (γLV), remains a widely accepted basis for developing wettability patterns. In contrast, we introduce a 'liquid-specific' wettability pattern through selectively sacrificing the slippery property against only low γLV (<30 mN m-1) liquids. This design includes a chemically reactive crystalline network of phase-transitioning polymer, which displays an effortless sliding of both low and high γLV liquids. Upon its strategic chemical modification, droplets of low γLV liquids fail to slide, rather spill arbitrarily on the tilted interface. In contrast, droplets of high γLV liquids continue to slide on the same modified interface. Interestingly, the phase-transition driven rearrangement of crystalline network allows to revert the slippery property against low γLV liquids. Here, we report a 'rewritable' and 'liquid-specific' wettability pattern for high throughput screening, separating, and remoulding non-aqueous liquids.

Sequential Infiltration Synthesis of Silicon Dioxide in Polymers with Ester Groups-Insight from In Situ Infrared Spectroscopy.

New strategies to synthesize nanometer-scale silicon dioxide (SiO2) patterns have drawn much attention in applications such as microelectronic and optoelectronic devices, membranes, and sensors, as we are approaching device dimensions shrinking below 10 nm. In this regard, sequential infiltration synthesis (SIS), a two-step gas-phase molecular assembly process that enables localized inorganic material growth in the targeted reactive domains of polymers, is an attractive process. In this work, we performed in situ Fourier transform infrared spectroscopy (FTIR) measurements during SiO2 SIS to investigate the reaction mechanism of trimethylaluminum (TMA) and tri(tert-pentoxy) silanol (TPS) precursors with polymers having ester functional groups (poly(methyl methacrylate) (PMMA), poly(ethyl methacrylate) (PEMA), polycaprolactone (PCL), and poly(t-butyl methacrylate) (PBMA)), for the purpose of growing patterned nanomaterials. The FTIR results show that for PMMA and PEMA, a lower percentage of functional groups participated in the reactions and formed weak and unstable complexes. In contrast, almost all functional groups in PCL and PBMA participated in the reactions and showed stable and irreversible interactions with TMA. We discovered that the amount of SiO2 formed is not directly correlated with the number of interacting functional groups. These insights into the SiO2 SIS mechanism will enable nanopatterning of SiO2 for low-dimensional applications.

Covalent crosslinking chemistry for controlled modulation of nanometric roughness and surface free energy.

Smooth interfaces embedded with low surface free energy allow effortless sliding of beaded droplets of selected liquids-with homogeneous wettability. Such slippery interfaces display low or moderate contact angles, unlike other extremely liquid repellent interfaces (e.g. superhydrophobic). These slippery interfaces emerged as a promising alternative to extremely liquid repellent hierarchically rough interfaces that generally suffer from instability under severe conditions, scattering of visible light because of the hierarchically rough interface, entrapment of fine solid particulates in their micro-grooves and so on. However, a controlled and precise modulation of surface free energy and nanometric roughness is essential for designing a more compelling solid and dry antifouling interface. Here, we have unprecedentedly demonstrated the ability of covalent cross-linking chemistry for precise and simultaneous modulation of both essential surface free energy (∼49 mN m-1 to ∼22 mN m-1) and roughness (root mean square roughness from 30 nm to 3 nm) of a solid interface for achieving liquid, substrate, and process independent, robust slippery properties. The strategic selection of ß-amino-ester linkage through a 1,4-conjugated addition reaction between amine and acrylate groups of a three component reaction mixture (dominated by a 61% (w/w) crosslinker) under ambient conditions provided a facile basis for associating various important and relevant properties-including self-cleaning ability, anti-smudge properties (against both water and oil-based inks), thermal stability (>300 °C), chemical stability, physical durability, optical transparency (∼95%) and so on. The embedded slippery properties of the coating remained unaffected at both low (0 °C) and high (100 °C) temperatures. Thus, the prepared coating would be appropriate to maintain the unperturbed performance of commercially available solar cell modules and other relevant objects under outdoor conditions.

Azolla Pinnata: Sustainable Floating Oil Cleaner of Water Bodies.

Various plant-based materials effectively absorb oil contaminants at the water/air interface. These materials showcase unparalleled efficiency in purging oil contaminants, encompassing rivers, lakes, and boundless oceans, positioning them as integral components of environmental restoration endeavors. In addition, they are biodegradable, readily available, and eco-friendly, thus making them a preferable choice over traditional oil cleaning materials. This study explores the phenomenal properties of the floating Azolla fern (Azolla pinnata), focusing on its unique hierarchical leaf surface design at both the microscale and nanoscale levels. These intricate structures endow the fern with exceptional characteristics, including superhydrophobicity, high water adhesion, and remarkable oil or organic solvent absorption capabilities. Azolla's leaf surface exhibits a rare combination of dual wettability, where hydrophilic spots on a superhydrophobic base enable the pinning of water droplets, even when positioned upside-down. This extraordinary property, known as the parahydrophobic state, is rare in floating plants, akin to the renowned Salvinia molesta, setting Azolla apart as a natural wonder. Submerged in water, Azolla leaves excel at absorbing light oils at the air-water interface, demonstrating a notable ability to extract high-density organic solvents. Moreover, Azolla's rapid growth, doubling in the area every 4-5 days, especially in flowing waters, positions it as a sustainable alternative to traditional synthetic oil-cleaning materials with long-term environmental repercussions. This scientific lead could pave the way for more environmentally friendly approaches to mitigate the negative impacts of oil spills and promote a cleaner water ecosystem.

Self-healable, Tolerant Superaerophobic Coating for Improving Electrochemical Hydrogen Production.

Gas-evolving electrodes often suffer from the blocking of catalytic active sites-due to unwanted and unavoidable adhesion of generated gas bubbles, which elevates the overpotential for the electrochemical hydrogen evolution reaction (HER)- by raising the resistance of the electrode. Here, a catalyst-free and self-healable superaerophobic coating having ultra-low bubble adhesion is introduced for achieving significantly depleted overpotentials of 209 and 506 mV at both low (50 mA cm-2) and high (500 mA cm-2) current densities, respectively, compared to a bare nickel-foam electrode. The optimized coating ensured an early detachment of the generated tiny (0.8 ± 0.1 mm) gas bubble-and thus, prevented the undesired rise in resistance of the coated electrode. The systematic association of physical (i.e., ionic interactions, H-bonding, etc.) cross-linkage, ß-amino ester type covalent cross-linkage and reinforced halloysite nano clay enables the design of such functional material embedded with essential characteristics-including improved mechanical (toughness of 63.7 kJ m-3, and tensile modulus of 26 kPa) property and chemical (extremes of pH (1 and 14), salinity, etc.) stability, rapid (<10 min) self-healing ability (even at alkaline condition) and desired bubble-wettability (bubble contact angle of 158.2 ± 0.2°) with ultralow force (4.2 ± 0.4 µN) of bubble adhesion.

Polymerization of monomer aggregates for tailoring and patterning water wettability.

An approach of 'polymerization of monomers in its aggregated form' is unprecedentedly introduced to (i) tailor the water wettability of fibrous and porous substrates from hydrophobicity to superhydrophobicity, and (ii) associate patterned wettability. A solution of selected monomers-i.e., alkyl acrylate in a good solvent (indicating high solubility; ethanol) was transferred into a bad solvent (refers to poor solubility; water) to achieve a stable dispersion of monomer aggregates of size <1 µm for deposition on fibrous and porous substrates. Its photopolymerization provided a durable coating with the ability to tailor the water wettability from 134° to 153°. Furthermore, a spatially selective photopolymerization process yielded a patterned interface of superhydrophilicity and superhydrophobicity. Such a facile chemical approach with the ability to provide a durable coating embedded with tailored and patterned wettability would be useful for various potential applications.

Resonant coupling of molecular excitons and optical anapoles in silicon nanosphere-J-aggregate heterostructures under vector beam illumination.

Resonant excitation of high-index dielectric nanostructures and their coupling with molecular excitons provide great opportunities for engineering adaptable platforms for hybrid functional optical devices. Here, we numerically calculate resonance coupling of nonradiating anapole states to molecular excitons within silicon nanosphere-J-aggregate heterostructures under illumination with radially polarized cylindrical vector beams. The results show that the resonance coupling is accompanied by a scattering peak around the exciton transition frequency, and the anapole state splits into a pair of anticrossing eigenmodes with a mode splitting energy of ≈200m e V. We also investigate the resonance coupling as a function of the J-aggregate parameters, such as thickness, exciton transition linewidth, and oscillator strength. Resonant coupling of the anapole states and J-aggregate heterostructures could be a promising platform for future nanophotonic applications such as in information processing and sensing.

Chemically selective raising and rolling of oil-droplets underwater: an equipment-free chemical sensing method.

A dual chemically reactive multilayer coating is rationally subjected to mono- and dual-functionalization through a 1,4-conjugate addition reaction at ambient conditions to depict the raising of the oil contact angle and rolling of a beaded oil-droplet underwater, respectively, only in the presence of targeted toxic chemicals (e.g. nitrite ion and hydrazine). Rational switching of the hydrophobic aromatic moiety into a hydrophilic moiety in the modified multilayer coatings via selected modified Griess reaction and Schiff base reaction contributed to the desired change in underwater oil-wettability and oil-adhesion. Eventually, this approach allowed equipment-free and naked-eye chemical sensing with high selectivity and sensitivity.

Lubricated Interfaces Enabling Simultaneous Pulsatile and Continuous Chemical Release Modes.

The release of chemicals following either pulsatile or continuous release modes is important for various potential applications, including programmed chemical reactions, mechanical actuation, and treatments of various diseases. However, the simultaneous application of both modes in a single material system has been challenging. Here, two chemical loading methods are reported in a liquid-crystal-infused porous surface (LCIPS) that enables both a pulsatile and continuous release of chemicals simultaneously. Specifically, chemicals loaded in the porous substrate exhibit a liquid crystal (LC) mesophase-dependent continuous release, whereas the chemicals dissolved in micrometer-sized aqueous droplets dispersed in the LC surface follow a pulsatile release activated by a phase transition. Moreover, the loading method of distinct molecules can be controlled to program their release mode. Finally, the pulsatile and continuous release of two distinct bioactive small molecules, tetracycline and dexamethasone, are demonstrated which display antibacterial and immunomodulatory activities for applications such as chronic wound healing and biomedical implant coating.

Design of a self-cleanable multilevel anticounterfeiting interface through covalent chemical modulation.

Counterfeit products have posed a significant threat to consumers safety and the global economy. To address this issue, extensive studies have been exploring the use of coatings with unclonable, microscale features for authentication purposes. However, the ease of readout, and the stability of these features against water, deposited dust, and wear, which are required for practical use, remain challenging. Here we report a novel class of chemically functionalizable coatings with a combination of a physically unclonable porous topography and distinct physiochemical properties (e.g., fluorescence, water wettability, and water adhesion) obtained through orthogonal chemical modifications (i.e., 1,4-conjugate addition reaction and Schiff-base reaction at ambient conditions). Unprecedentedly, a self-cleanable and physically unclonable coating is introduced to develop a multilevel anticounterfeiting interface. We demonstrate that the authentication of the fluorescent porous topography can be verified using deep learning. More importantly, the spatially selective chemical modifications can be read with the naked eye via underwater exposure and UV light illumination. Overall, the results reported in this work provide a facile basis for designing functional surfaces capable of independent and multilevel decryption of authenticity.

Reactive Multilayer Coating As Versatile Nanoarchitectonics for Customizing Various Bioinspired Liquid Wettabilities.

In last few decades, multilayer coatings have achieved enormous attention owing to their unique ability to tune thickness, topography, and chemical composition for developing various functional materials. Such multilayer coatings were mostly and conventionally derived by following a simple layer-by-layer (LbL) deposition process through the strategic use of electrostatic interactions, hydrogen bonding, host-guest interactions, covalent bonding, etc. In the conventional design of multilayer coatings, the chemical composition and morphology of coatings are modulated during the process of multilayer constructions. In such an approach, the postmodulations of the porous multilayers with different and desired chemistries are challenging to achieve due to the lack of availability of readily and selectively reactive moieties. Recently, the design of readily and selectively reactive multilayer coatings (RMLCs) provided a facile basis for postmodulating the prepared coating with various desired chemistries. In fact, by taking advantage of the inherent ability of co-optimizing the topography and various chemistries in porous RMLCs, different durable bioinspired liquid wettabilities (i.e., superhydrophobicity, underwater superoleophobicity, underwater superoleophilicity, slippery property, etc.) were successfully derived. Such interfaces have enormous potential in various prospective applications. In this review, we intend to give an overview of the evolution of LbL multilayer coatings and their synthetic strategies and discuss the key advantages of porous RMLCs in terms of achieving and controlling wettability properties. Recent attempts toward various applications of such multilayer coatings that are strategically embedded with different desired liquid wettabilities will be emphasized.

Non-Fluorinated and Robust Superhydrophobic Modification on Covalent Organic Framework for Crude-Oil-in-Water Emulsion Separation.

Covalent organic frameworks (COFs) having high specific surface area, tunable pore size and high crystallinity are mostly post modified following fluorine-based and complex synthetic approaches to achieve a bio-inspired liquid wettability, i.e. superhydrophobicity. Herein, a facile, non-fluorinated and robust chemical approach is introduced for tailoring the water wettability of a new COF-which was prepared through Schiff-base condensation reaction. A silane precursor was readily reacted with selected alkyl acrylates through 1,4-conjugate addition reaction, prior to grafting on the prepared C4-COF for tailoring different water wettability-including robust superhydrophobicity. The superhydrophobic C4-COF (SH-C4-COF) that displayed significantly enhanced (>5 times; from 220 wt. % to 1156 wt. %) oil-absorption capacity, was extended to address the relevant challenges of "oil-in-water" emulsion separation, rapidly (<1 minute) and repetitively (50 times) at diverse and harsh conditions.

Role of chemistry in bio-inspired liquid wettability.

Chemistry and topography are the two distinct available tools for customizing different bio-inspired liquid wettability including superhydrophobicity, superamphiphobicity, underwater superoleophobicity, underwater superoleophilicity, and liquid infused slippery property. In nature, various living species possessing super and special liquid wettability inherently comprises of distinctly patterned surface topography decorated with low/high surface energy. Inspired from the topographically diverse natural species, the variation in surface topography has been the dominant approach for constructing bio-inspired antiwetting interfaces. However, recently, the modulation of chemistry has emerged as a facile route for the controlled tailoring of a wide range of bio-inspired liquid wettability. This review article aims to summarize the various reports published over the years that has elaborated the distinctive importance of both chemistry and topography in imparting and modulating various bio-inspired wettability. Moreover, this article outlines some obvious advantages of chemical modulation approach over topographical variation. For example, the strategic use of the chemical approach has allowed the facile, simultaneous, and independent tailoring of both liquid wettability and other relevant physical properties. We have also discussed the design of different antiwetting patterned and stimuli-responsive interfaces following the strategic and precise alteration of chemistry for various prospective applications.

Design of a Super-Liquid Crystal-Phobic Coating for Immobilizing Liquid Crystal µ-Droplets─Without Affecting Their Sensitivity.

The aqueous interface of nematic liquid crystal (LC) that undergoes a triggered change in ordering transition of mesogens under an appropriate stimulus has emerged as an important tool for various relevant applications. Further, the confinement of LC into a micrometer dimension appeared to be a facile approach for improving their relevant features and performance. However, the optical characterization of ordering transition in a single micrometer-sized, bare, and free-floating LC droplet in the aqueous phase is an extremely challenging task due to unavoidable Brownian motion, which limits its scope for practical applications. Here, we exploited the 1,4-conjugate addition reaction to report a multilayer coating of a reactive nanocomplex that displayed an extreme repellence to beaded LC droplets with tailored adhesive force through the association of adequate orthogonal chemical modifications with glucamine and selected alkyl acrylates. Further, a spatially selective underwater adhesive super-LC-phobic pattern on a hydrophobic background was developed for immobilizing bare and micrometer-sized LC droplets from their aqueous dispersion without having any arbitrary spillage of the aqueous medium. The settled micrometer-sized LC droplets remained efficient for the triggered change in ordering transition from bipolar (having boojum defects at poles) to radial (with a single defect in the center) configuration. Eventually, a simple and fundamentally distinct chemical strategy of immobilizing a soft and functional material by associating bio-inspired wettability allowed to demonstrate the repetitive triggered LC ordering transition in a single and bare LC droplet.

Multiplexed Covalent Patterns on Double-Reactive Porous Coating.

We have conceptualized and demonstrated an approach based on the combination of hydrophobicity, a substrate-independent dip coating as porous material with double residual chemical reactivities for implementing multiplexed, miniaturized and unclonable bulk-infused patterns of different fluorophores following distinct reaction pathways. The embedded hydrophobicity (∼102°) restricted the unwanted spreading of beaded aqueous ink on the coating. The constructions of micropatterns on porous dip-coating via ink-jet printing or microchannel cantilever spotting offered orthogonal read-out and remained readable even after removal of the exterior of the coating.

Designing a Network of Crystalline Polymers for a Scalable, Nonfluorinated, Healable and Amphiphobic Solid Slippery Interface.

The fluorinated-liquid infused amphiphobic slippery interfaces exhibiting superior sliding of the beaded oil/water droplets, often suffer from durability and contamination issues. Here, the ability of 1) hexagonal packing of hydrocarbon sides in a selected "comb-like" polymer and 2) its reversible phase transition at 51 °C was rationally exploited to achieve temperature-assisted rapid (<1 minute) and repetitive (50 times) self-healable amphiphobic solid-slippery coating on both planar and geometrically-complex substrates. The selected "comb-like" polymer was strategically infused in a porous, hydrophilic and thick (≈4.8 µm) polymeric coating. The resultant solid and smooth interface exhibited sliding of beaded droplets of various liquids, including droplets of water, polar (ethanol, 1-propanol, 1-hexanol, DMSO, DMF), and non-polar (decane, dodecane, diiodomethane) organic solvents, edible (vegetable oil), motor, engine (petrol, diesel, kerosene) and crude oils.

Dually reactive multilayer coatings enable orthogonal manipulation of underwater superoleophobicity and oil adhesion via post-functionalization.

Fish scale-inspired underwater superoleophobic coatings with low oil adhesion can be achieved through the creation of hierarchical surface topography on water-compatible materials (including polymeric hydrogels, metal oxides, and electrostatic multilayers). While promising, these method do not allow for the underwater superoleophobicity and oil adhesion to be independently tuned, limiting their potential applications. Here we report the design of a conceptually novel class of coatings, dually reactive multilayer coatings, whose underwater superoleophobicity and oil adhesion can be independently tuned through the orthogonal functionalization of two types of reactive moieties at ambient conditions. Moreover, the cooperative assembly of amphiphiles on the modified underwater superoleophobic coating gives rise to a switchable oil adhesion while retaining the extreme oil-repellency (advancing oil contact angle >165°). Interestingly, the reversible change in the oil adhesion of the underwater superoleophobic coatings depends on the interplay between the molecular structure and concentration of the amphiphiles and the pH of the aqueous solution. Building on these findings, we developed superoleophobic sensors that enable the real-time and naked eye identification of (1) the charge of synthetic ionic surfactants and (2) the concentration of bile acids. Overall, the results reported in this work provide design principles by which molecular self-assembly and oil adhesion can be coupled at underwater superoleophobic surfaces, and hint at principles by which physiologically important amphiphiles and metabolites can be rapidly sensed with the naked eye using our novel class of superoleophobic surfaces.

Stimuli-Responsive Liquid-Crystal-Infused Porous Surfaces for Manipulation of Underwater Gas Bubble Transport and Adhesion.

Biomimetic artificial surfaces that enable the manipulation of gas bubble mobility have been explored in a wide range of applications in nanomaterial synthesis, surface defouling, biomedical diagnostics, and therapeutics. Although many superhydrophobic surfaces and isotropic-lubricant-infused porous surfaces have been developed to manipulate gas bubbles, the simultaneous control over the adhesion and transport of gas bubbles underwater remains a challenge. Thermotropic liquid crystals (LCs), a class of structured fluids, provide an opportunity to tune the behavior of gas bubbles through LC mesophase transitions using a variety of external stimuli. Using this central idea, the design and synthesis of LC-infused porous surfaces (LCIPS) is reported and the effects of the LC mesophase on the transport and adhesion of gas bubbles on LCIPS immersed in water elucidated. LCIPS are demonstrated to be a promising class of surfaces with an unprecedented level of responsiveness and functionality, which enables the design of cyanobacteria-inspired object movement, smart catalysts, and bubble gating devices to sense and sort volatile organic compounds and control oxygen levels in biomimetic cell cultures.

Design of 'tolerant and hard' superhydrophobic coatings to freeze physical deformation.

While the development of mechanically durable and abrasion tolerant superhydrophobicity on a rigid substrates itself remains a highly challenging task, the design of superhydrophobic coatings that can restrict both the tensile and compressive deformations of soft and deformable substrates is unprecedented-and such an approach would be of potential interest in various applied and fundamental contexts. In this communication, a reaction mixture was developed following a simple 1,4-conjugate addition reaction between selected small molecules and appropriate crosslinkers for achieving 'tolerant and hard' superhydrophobicity-which is not just capable of surviving under severe conditions-but also restricts both the tensile and compressive deformations of the selected soft substrates. The compressive and tensile moduli of the selected soft substrates increased by 2.2 × 104% and 1.8 × 104%, respectively, after the deposition of the appropriate reaction mixtures. Moreover, the integration of the crosslinkers in the reaction mixture provided a facile basis to resist the physical erosion/rupture of the selected soft substrates under severe abrasive conditions. Thus, a simple and elegant chemical approach not only controlled the mechanical properties of the porous and fibrous soft substrates under ambient conditions-but also provided highly tolerant superhydrophobicity-which likely leads to various outdoor applications.

Rapid and Scalable Synthesis of a Vanillin-Based Organogelator and Its Durable Composite for a Comprehensive Remediation of Crude-Oil Spillages.

Phase-selective organogelators (PSOGs) that have immense potential in effective oil/water separation, antifouling coating, ice-repellent coating, and so on are often synthesized by following complex and multistep synthesis procedures that involve additional and tedious purification steps. On the other side, a comprehensive, selective, environmentally friendly, and energy-efficient separation of different and complex forms of oil spillages (e.g., floating oil or oil-in-water emulsions) from contaminated aqueous phase is challenging to achieve based on earlier-reported PSOGs and their composites. Here, vanillin, a naturally abundant molecule, is unprecedentedly exploited to synthesize a purified PSOG (with a yield of 97%) by adopting a catalyst-free, single-step, and rapid (<2 min) synthesis process under ambient conditions. The Schiff's base reaction between the aldehyde group of vanillin and the primary amine group of octadecylamine provided the desired and purified PSOG-without demanding any additional purification processes (e.g., column chromatography). The appropriate coexistence of the imine linkage, hydrocarbon tail, and hydroxyl group in the vanillin-derived organogelator (VDOG) played an important role in achieving a self-standing organogel that sustained ∼60 times the external load of its weight-without having any noticeable physical deformation. Further, an appropriate and facile integration of the synthesized VDOG with a commercially available biodegradable porous and spongy matrix (i.e., polyurethane sponge) allowed us to develop an oil-selective absorbent with (1) enhanced water repellency (140°) and (2) superior oil-absorption capacity (i.e., 55.2 times its own weight). Such composite material remained durable for repetitive (at least for 50 cycles) and distillation-free separation/recovery of crude oil at practically relevant severe and diverse settings. Thereafter, the synthesized VDOG was successfully and unprecedentedly extended to demonstrate rapid, facile, and efficient separation of surfactant-stabilized oil-in-water emulsions.