Super-Droplet-Repellent Carbon-Based Printable Perovskite Solar Cells.

Despite attractive cost-effectiveness, scalability, and superior stability, carbon-based printable perovskite solar cells (CPSCs) still face moisture-induced degradation that limits their lifespan and commercial potential. Here, the moisture-preventing mechanisms of thin nanostructured super-repellent coating (advancing contact angle >167° and contact angle hysteresis 7°) integrated into CPSCs are investigated for different moisture forms (falling water droplets vs water vapor vs condensed water droplets). It is shown that unencapsulated super-repellent CPSCs have superior performance under continuous droplet impact for 12 h (rain falling experiments) compared to unencapsulated pristine (uncoated) CPSCs that degrade within seconds. Contrary to falling water droplets, where super-repellent coating serves as a shield, water vapor is found to physisorb through porous super-repellent coating (room temperature and relative humidity, RH 65% and 85%) that increase the CPSCs performance for 21% during ≈43 d similarly to pristine CPSCs. It is further shown that water condensation forms within or below the super-repellent coating (40 °C and RH 85%), followed by chemisorption and degradation of CPSCs. Because different forms of water have distinct effects on CPSC, it is suggested that future standard tests for repellent CPSCs should include rain falling and condensate formation tests. The findings will thus inspire the development of super-repellent coatings for moisture prevention.

Toward vanishing droplet friction on repellent surfaces.

Superhydrophobic surfaces are often seen as frictionless materials, on which water is highly mobile. Understanding the nature of friction for such water-repellent systems is central to further minimize resistance to motion and energy loss in applications. For slowly moving drops, contact-line friction has been generally considered dominant on slippery superhydrophobic surfaces. Here, we show that this general rule applies only at very low speed. Using a micropipette force sensor in an oscillating mode, we measure the friction of water drops approaching or even equaling zero contact-line friction. We evidence that dissipation then mainly stems from the viscous shearing of the air film (plastron) trapped under the liquid. Because this force is velocity dependent, it can become a serious drag on surfaces that look highly slippery from quasi-static tests. The plastron thickness is found to be the key parameter that enables the control of this special friction, which is useful information for designing the next generation of ultraslippery water-repellent coatings.

Through-Drop Imaging of Liquid-Solid Interfaces: From Contact Angle Variations Along the Droplet Perimeter to Mapping of Contact Angles Across a Surface.

When a droplet interacts with a water-repellent surface, its triple-phase contact line typically exhibits varying contact angles, which can vary from point-to-point across the surface. Consequently, measuring the contact angles along the contact line would provide a better representation of the wetting properties of the surface than a single average contact angle. However, an effective method for estimating the local contact angle along the contact line on opaque hydrophobic surfaces is currently lacking. Here we present a method that combines through-drop imaging of the wetting interface during a sliding experiment with Finite Element Modeling of the droplet to estimate contact angle values along the contact line. Using this method, the mean advancing and receding contact angles were measured on four types of hydrophobic samples with contact angles between 99 and 178.9°. The method was further used to produce detailed advancing and receding contact angle maps of surfaces with wetting patterns with an unprecedented resolution of 3 µm.

Droplet slipperiness despite surface heterogeneity at molecular scale.

Friction determines whether liquid droplets slide off a solid surface or stick to it. Surface heterogeneity is generally acknowledged as the major cause of increased contact angle hysteresis and contact line friction of droplets. Here we challenge this long-standing premise for chemical heterogeneity at the molecular length scale. By tuning the coverage of self-assembled monolayers (SAMs), water contact angles change gradually from about 10° to 110° yet contact angle hysteresis and contact line friction are low for the low-coverage hydrophilic SAMs as well as high-coverage hydrophobic SAMs. Their slipperiness is not expected based on the substantial chemical heterogeneity of the SAMs featuring uncoated areas of the substrate well beyond the size of a water molecule as probed by metal reactants. According to molecular dynamics simulations, the low friction of both low- and high-coverage SAMs originates from the mobility of interfacial water molecules. These findings reveal a yet unknown and counterintuitive mechanism for slipperiness, opening new avenues for enhancing the mobility of droplets.

pH-Responsive Near-Infrared Emitting Gold Nanoclusters.

Near-infrared (NIR) fluorophores with pH-responsive properties suggest merits in biological analyses. This work establishes a general and effective method to obtain pH-responsive NIR emissive gold nanoclusters by introducing aliphatic tertiary amine (TA) groups into the ligands. Computational study suggests that the pH-responsive NIR emission is associated with electronic structure change upon protonation and deprotonation of TA groups. Photo-induced electron transfer between deprotonated TA groups and the surface Au-S motifs of gold nanoclusters can disrupt the radiative transitions and thereby decrease the photoluminescence intensity in basic environments (pH=7-11). By contrast, protonated TA groups curb the electron transfer and restore the photoluminescence intensity in acidic environments (pH=4-7). The pH-responsive NIR-emitting gold nanoclusters serve as a specific and sensitive probe for the lysosomes in the cells, offering non-invasive emissions without interferences from intracellular autofluorescence.

Long-term stability of aerophilic metallic surfaces underwater.

Aerophilic surfaces immersed underwater trap films of air known as plastrons. Plastrons have typically been considered impractical for underwater engineering applications due to their metastable performance. Here, we describe aerophilic titanium alloy (Ti) surfaces with extended plastron lifetimes that are conserved for months underwater. Long-term stability is achieved by the formation of highly rough hierarchically structured surfaces via electrochemical anodization combined with a low-surface-energy coating produced by a fluorinated surfactant. Aerophilic Ti surfaces drastically reduce blood adhesion and, when submerged in water, prevent adhesion of bacteria and marine organisms such as barnacles and mussels. Overall, we demonstrate a general strategy to achieve the long-term stability of plastrons on aerophilic surfaces for previously unattainable underwater applications.

Flattened and Wrinkled Encapsulated Droplets: Shape Morphing Induced by Gravity and Evaporation.

We report surprising morphological changes of suspension droplets (containing class II hydrophobin protein HFBI from Trichoderma reesei in water) as they evaporate with a contact line pinned on a rigid solid substrate. Both pendant and sessile droplets display the formation of an encapsulating elastic film as the bulk concentration of solute reaches a critical value during evaporation, but the morphology of the droplet varies significantly: for sessile droplets, the elastic film ultimately crumples in a nearly flattened area close to the apex while in pendant droplets, circumferential wrinkling occurs close to the contact line. These different morphologies are understood through a gravito-elastocapillary model that predicts the droplet morphology and the onset of shape changes, as well as showing that the influence of the direction of gravity remains crucial even for very small droplets (where the effect of gravity can normally be neglected). The results pave the way to control droplet shape in several engineering and biomedical applications.

Design of Fluoro-Free Surfaces Super-Repellent to Low-Surface-Tension Liquids.

Super-liquid-repellent surfaces feature high liquid contact angles and low sliding angles find key applications in anti-fouling and self-cleaning. While repellency for water is easily achieved with hydrocarbon functionalities, repellency for many low-surface-tension liquids (down to 30 mN m-1 ) still requires perfluoroalkyls (a persistent environmental pollutant and bioaccumulation hazard). Here, the scalable room-temperature synthesis of stochastic nanoparticle surfaces with fluoro-free moieties is investigated. Silicone (dimethyl and monomethyl) and hydrocarbon surface chemistries are benchmarked against perfluoroalkyls, assessed using model low-surface-tension liquids (ethanol-water mixtures). It is discovered that both hydrocarbon- and dimethyl-silicone-based functionalization can achieve super-liquid-repellency down to 40-41 mN m-1 and 32-33 mN m-1 , respectively (vs 27-32 mN m-1 for perfluoroalkyls). The dimethyl silicone variant demonstrates superior fluoro-free liquid repellency likely due to its denser dimethyl molecular configuration. It is shown that perfluoroalkyls are not necessary for many real-world scenarios requiring super-liquid-repellency. Effective super-repellency of different surface chemistries against different liquids can be adequately predicted using empirically verified phase diagrams. These findings encourage a liquid-centric design, i.e., tailoring surfaces for target liquid properties. Herein, key guidelines are provided for achieving functional yet sustainably designed super-liquid-repellency.

Repurposing host-guest chemistry to sequester virulence and eradicate biofilms in multidrug resistant Pseudomonas aeruginosa and Acinetobacter baumannii.

The limited diversity in targets of available antibiotic therapies has put tremendous pressure on the treatment of bacterial pathogens, where numerous resistance mechanisms that counteract their function are becoming increasingly prevalent. Here, we utilize an unconventional anti-virulence screen of host-guest interacting macrocycles, and identify a water-soluble synthetic macrocycle, Pillar[5]arene, that is non-bactericidal/bacteriostatic and has a mechanism of action that involves binding to both homoserine lactones and lipopolysaccharides, key virulence factors in Gram-negative pathogens. Pillar[5]arene is active against Top Priority carbapenem- and third/fourth-generation cephalosporin-resistant Pseudomonas aeruginosa and Acinetobacter baumannii, suppressing toxins and biofilms and increasing the penetration and efficacy of standard-of-care antibiotics in combined administrations. The binding of homoserine lactones and lipopolysaccharides also sequesters their direct effects as toxins on eukaryotic membranes, neutralizing key tools that promote bacterial colonization and impede immune defenses, both in vitro and in vivo. Pillar[5]arene evades both existing antibiotic resistance mechanisms, as well as the build-up of rapid tolerance/resistance. The versatility of macrocyclic host-guest chemistry provides ample strategies for tailored targeting of virulence in a wide range of Gram-negative infectious diseases.

Omniphobic liquid-like surfaces.

Liquid-repellent surfaces, especially smooth solid surfaces with covalently grafted flexible polymer brushes or alkyl monolayers, are the focus of an expanding research area. Surface-tethered flexible species are highly mobile at room temperature, giving solid surfaces a unique liquid-like quality and unprecedented dynamical repellency towards various liquids regardless of their surface tension. Omniphobic liquid-like surfaces (LLSs) are a promising alternative to air-mediated superhydrophobic or superoleophobic surfaces and lubricant-mediated slippery surfaces, avoiding fabrication complexity and air/lubricant loss issues. More importantly, the liquid-like molecular layer controls many important interface properties, such as slip, friction and adhesion, which may enable novel functions and applications that are inaccessible with conventional solid coatings. In this Review, we introduce LLSs and their inherent dynamic omniphobic mechanisms. Particular emphasis is given to the fundamental principles of surface design and the consequences of the liquid-like nature for task-specific applications. We also provide an overview of the key challenges and opportunities for omniphobic LLSs.

Through-drop imaging of moving contact lines and contact areas on opaque water-repellent surfaces.

A myriad of natural surfaces such as plant leaves and insect wings can repel water and remain unwetted inspiring scientists and engineers to develop water-repellent surfaces for various applications. Those natural and artificial water-repellent surfaces are typically opaque, containing micro- and nano-roughness, and their wetting properties are determined by the details at the actual liquid-solid interface. However, a generally applicable way to directly observe moving contact lines on opaque water-repellent surfaces is missing. Here, we show that the advancing and receding contact lines and corresponding contact area on micro- and nano-rough water-repellent surfaces can be readily and reproducibly quantified using a transparent droplet probe. Combined with a conventional optical microscope, we quantify the progression of the apparent contact area and apparent contact line irregularity in different types of superhydrophobic silicon nanograss surfaces. Contact angles near 180° can be determined with an uncertainty as low as 0.2°, that a conventional contact angle goniometer cannot distinguish. We also identify the pinning/depinning sequences of a pillared model surface with excellent repeatability and quantify the progression of the apparent contact interface and contact angle of natural plant leaves with irregular surface topography.

Compressibility and porosity modulate the mechanical properties of giant gas vesicles.

Gas vesicles used as contrast agents for noninvasive ultrasound imaging must be formulated to be stable, and their mechanical properties must be assessed. We report here the formation of perfluoro-n-butane microbubbles coated with surface-active proteins that are produced by filamentous fungi (hydrophobin HFBI from Trichoderma reesei). Using pendant drop and pipette aspiration techniques, we show that these giant gas vesicles behave like glassy polymersomes, and we discover novel gas extraction regimes. We develop a model to analyze the micropipette aspiration of these compressible gas vesicles and compare them to incompressible liquid-filled vesicles. We introduce a sealing parameter to characterize the leakage of gas under aspiration through the pores of the protein coating. Utilizing this model, we can determine the elastic dilatation modulus, surface viscosity, and porosity of the membrane. These results demonstrate the engineering potential of protein-coated bubbles for echogenic and therapeutic applications and extend the use of the pipette aspiration technique to compressible and porous systems.

Bright and Photostable Fluorescent Metal Nanocluster Supraparticles from Invert Emulsions.

Fluorescent supraparticles of gold, silver and copper nanoclusters are synthesized by simply drying of invert emulsions, resulting in a dozen-fold increase in photoluminescence quantum yield (up to ≈80 %) and a significant improvement in photostability. The inhibition of the ligand twisting during the intramolecular charge transfer is found to be responsible for the enhancement, especially for the gold nanocluster supraparticles. This research provides a general, flexible, and easy method for producing highly luminescent and photostable metal nanocluster-based materials that promise practical applications in white-light-emitting diodes.

Probing the Free Energy of Small Water Clusters: Revisiting Classical Nucleation Theory.

By addressing the defects in classical nucleation theory (CNT), we develop an approach for extracting the free energy of small water clusters from nucleation rate experiments without any assumptions about the form of the cluster free energy. For temperatures higher than ∼250 K, the extracted free energies from experimental data points indicate that their ratio to the free energies predicted by CNT exhibits nonmonotonic behavior as the cluster size changes. We show that this ratio increases from almost zero for monomers and passes through (at least) one maximum before approaching one for large clusters. For temperatures lower than ∼250 K, the behavior of the ratio between extracted energies and CNT's prediction changes; it increases with cluster size, but it remains below one for almost all of the experimental data points. We also applied a state-of-the-art quantum mechanics model to calculate free energies of water clusters (2-14 molecules); the results support the observed change in behavior based on temperature, albeit for temperatures above and below ∼298 K. We compared two different model chemistries, DLPNO-CCSD(T)/CBS//ωB97xD/6-31++G** and G3, against each other and the experimental value for formation of the water dimer.

High-resolution crystal structure of a 20 kDa superfluorinated gold nanocluster.

Crystallization of atomically precise nanoclusters is gaining increasing attention, due to the opportunity of elucidating both intracluster and intercluster packing modes, and exploiting the functionality of the resulting highly pure crystallized materials. Herein, we report the design and single-crystal X-ray structure of a superfluorinated 20 kDa gold nanocluster, with an Au25 core coated by a shell of multi-branched highly fluorinated thiols (SF27) resulting in almost 500 fluorine atoms, i.e., ([Au25(SF27)18]0). The cluster shows a switchable solubility in the fluorous phase. X-ray analysis and computational studies reveal the key role of both intracluster and intercluster F···F contacts in driving [Au25(SF27)18]0 crystal packing and stabilization, highlighting the ability of multi-branched fluorinated thiols to endow atomically precise nanoclusters with remarkable crystallogenic behavior.

Solid-state polymer adsorption for surface modification: The role of molecular weight.

HYPOTHESIS: Solid-state polymer adsorption offers a distinct approach for surface modification. These ultrathin, so-called Guiselin layers can easily be obtained by placing a polymer melt in contact with an interface, followed by a removal of the non-adsorbed layer with a good solvent. While the mechanism of formation has been well established for Guiselin layers, their stability, crucial from the perspective of materials applications, is not. The stability is a trade-off in the entropic penalty between cooperative detachment of the number of segments directly adsorbed on the substrate and consecutively pinned monomers. EXPERIMENTS: Experimental model systems of Guiselin layers of polystyrene (PS) on silicon wafers with native oxide layer on top were employed. The stability of the adsorbed layers was studied as a function of PS molecular weight and polydispersibility by various microscopic and spectroscopic tools as well as quasi-static contact angle measurements. FINDINGS: Adsorbed layers from low molecular weight PS were disrupted with typical spinodal decomposition patterns whereas high molecular weight (>500 kDa) PS resulted in stable, continuous layers. Moreover, we show that Guiselin layers offer an enticing way to modify a surface, as demonstrated by adsorbed PS that imparts a hydrophobic character to initially hydrophilic silicon wafers.

3D Printing of Superhydrophobic Objects with Bulk Nanostructure.

The rapid development of 3D printing (or additive manufacturing) technologies demands new materials with novel properties and functionalities. Superhydrophobic materials, owing to their ultralow water adhesion, self-cleaning, anti-biofouling, or superoleophilic properties are useful for myriad applications involving liquids. However, the majority of the methods for making superhydrophobic surfaces have been based on surface functionalization and coatings, which are challenging to apply to 3D objects. Additionally, these coatings are vulnerable to abrasion due to low mechanical stability and limited thickness. Here, a new materials concept and methodology for 3D printing of superhydrophobic macroscopic objects with bulk nanostructure and almost unlimited geometrical freedom is presented. The method is based on a specific ink composed of hydrophobic (meth)acrylate monomers and porogen solvents, which undergoes phase separation upon photopolymerization to generate inherently nanoporous and superhydrophobic structures. Using a desktop Digital Light Processing printer, superhydrophobic 3D objects with complex shapes are demonstrated, with ultralow and uniform water adhesion measured with scanning droplet adhesion microscopy. It is shown that the 3D-printed objects, owing to their nanoporous structure throughout the entire volume, preserve their superhydrophobicity upon wear damage. Finally, a superhydrophobic 3D-printed gas-permeable and water-repellent microfluidic device and a hierarchically structured 3D-printed super-oil-absorbent are demonstrated.

Force-Based Wetting Characterization of Stochastic Superhydrophobic Coatings at Nanonewton Sensitivity.

Superhydrophobic coatings have extraordinary properties like self-cleaning and staying dry, and have recently appeared on industrial and consumer markets. The stochastic nature of the coating components and coating processes (e.g., spraying, painting) affects the uniformity of the water repellency across the coated substrate. The wetting properties of those coatings are typically quantified on macroscale using contact angle goniometry (CAG). Here, highly sensitive force-based methods, scanning droplet adhesion microscopy (SDAM), and micropipette force sensor (MFS), are used, to quantify the microscale heterogeneity in the wetting properties of stochastic superhydrophobic coatings with irregular surface topography that cannot be investigated by CAG. By mapping the wetting adhesion forces with SDAM and friction forces with MFS, it is demonstrated that even the best coatings on the market are prone to heterogeneities that induce stick-slip motion of droplets. Thus, owing to their high spatial and force resolution, the advantages of these techniques over CAG are demonstrated.