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.

Design of robust superhydrophobic surfaces.

The ability of superhydrophobic surfaces to stay dry, self-clean and avoid biofouling is attractive for applications in biotechnology, medicine and heat transfer1-10. Water droplets that contact these surfaces must have large apparent contact angles (greater than 150 degrees) and small roll-off angles (less than 10 degrees). This can be realized for surfaces that have low-surface-energy chemistry and micro- or nanoscale surface roughness, minimizing contact between the liquid and the solid surface11-17. However, rough surfaces-for which only a small fraction of the overall area is in contact with the liquid-experience high local pressures under mechanical load, making them fragile and highly susceptible to abrasion18. Additionally, abrasion exposes underlying materials and may change the local nature of the surface from hydrophobic to hydrophilic19, resulting in the pinning of water droplets to the surface. It has therefore been assumed that mechanical robustness and water repellency are mutually exclusive surface properties. Here we show that robust superhydrophobicity can be realized by structuring surfaces at two different length scales, with a nanostructure design to provide water repellency and a microstructure design to provide durability. The microstructure is an interconnected surface frame containing 'pockets' that house highly water-repellent and mechanically fragile nanostructures. This surface frame acts as 'armour', preventing the removal of the nanostructures by abradants that are larger than the frame size. We apply this strategy to various substrates-including silicon, ceramic, metal and transparent glass-and show that the water repellency of the resulting superhydrophobic surfaces is preserved even after abrasion by sandpaper and by a sharp steel blade. We suggest that this transparent, mechanically robust, self-cleaning glass could help to negate the dust-contamination issue that leads to a loss of efficiency in solar cells. Our design strategy could also guide the development of other materials that need to retain effective self-cleaning, anti-fouling or heat-transfer abilities in harsh operating environments.

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.

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.

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.

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.

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.

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.

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.

Luminescent Gold Nanocluster-Methylcellulose Composite Optical Fibers with Low Attenuation Coefficient and High Photostability.

Because of their lightweight structure, flexibility, and immunity to electromagnetic interference, polymer optical fibers (POFs) are used in numerous short-distance applications. Notably, the incorporation of luminescent nanomaterials in POFs offers optical amplification and sensing for advanced nanophotonics. However, conventional POFs suffer from nonsustainable components and processes. Furthermore, the traditionally used luminescent nanomaterials undergo photobleaching, oxidation, and they can be cytotoxic. Therefore, biopolymer-based optical fibers containing nontoxic luminescent nanomaterials are needed, with efficient and environmentally acceptable extrusion methods. Here, such an approach for fibers wet-spun from aqueous methylcellulose (MC) dispersions under ambient conditions is demonstrated. Further, the addition of either luminescent gold nanoclusters, rod-like cellulose nanocrystals or gold nanocluster-cellulose nanocrystal hybrids into the MC matrix furnishes strong and ductile composite fibers. Using cutback attenuation measurement, it is shown that the resulting fibers can act as short-distance optical fibers with a propagation loss as low as 1.47 dB cm-1 . The optical performance is on par with or even better than some of the previously reported biopolymeric optical fibers. The combination of excellent mechanical properties (Young's modulus and maximum strain values up to 8.4 GPa and 52%, respectively), low attenuation coefficient, and high photostability makes the MC-based composite fibers excellent candidates for multifunctional optical fibers and sensors.

Tunable and Magnetic Thiol-ene Micropillar Arrays.

Tunable and responsive surfaces offer routes to multiple functionalities ranging from superhydrophobic surfaces to controlled adhesion. Inspired by cilia structure in the respiratory pathway, magnetically responsive periodic arrays of flexible and magnetic thiol-ene micropillars are fabricated. Omnidirectional collective bending of the pillar array in magnetic field is shown. Local non-contact actuation of a single pillar is achieved using an electromagnetic needle to probe the responsiveness and the elastic properties of the pillars by comparing the effect of thiol-ene crosslinking density to pillar bending. The suitable thiol-ene components for flexible and stiff magnetic micropillars and the workable range of thiol-to-allyl ratio are identified. The wettability of the magnetic pillars can be tailored by chemical and topography modification of the pillar surface. Low-surface-energy self-assembled monolayers are grafted by UV-assisted surface activation, which is also used for surface topography modification by covalent bonding of micro- and nanoparticles to the pillar surface. The modified thiol-ene micopillars are resistant to capillarity-driven collapse and they exhibit low contact angle hysteresis, allowing water droplet motion driven by repeated bending and recovery of the magnetic pillars in an external magnetic field. Transport of polyethylene microspheres is also demonstrated.

Uncertainties in contact angle goniometry.

The most widely used method to quantify the wetting properties of surfaces is by measuring contact angles. Even though contact angle goniometry is a powerful technique for characterizing wetting properties, it is not accurate for very hydrophobic surfaces. As the technique relies on image processing, it has inherent errors due to optical limitations, especially near the three-phase contact line. This leads to uncertainties in the positioning of the baseline, which can cause large errors in the measured contact angles. In this paper, we systematically evaluate these errors both theoretically and experimentally, focusing on the importance of image resolution. For ∼9 microliter droplet, displacement of the baseline by a single pixel leads to errors of approximately ±0.5° to ±1° for contact angles up to 150°, and errors increase rapidly in the superhydrophobic regime, up to ±8°. The error in the contact angle can be slightly reduced by increasing the image resolution, but cannot be eliminated entirely.

Nanoliter deposition on star-shaped hydrophilic-superhydrophobic patterned surfaces.

Nanoliter sized droplet deposition has gained increasing importance in many biomedical, chemical, and microfluidic applications and in materials synthesis. In this paper, we report a simple method for rapid and high-throughput deposition of nanoliter-sized droplets by dragging a larger droplet on star-shaped hydrophilic-superhydrophobic patterned surfaces. Dragging a droplet on the patterned surface causes water to adhere to hydrophilic patterns. As the larger mother droplet detaches from a star-shaped pattern, a small daughter droplet is deposited on the pattern. Star-shaped hydrophilic patterns with a distinct number of spikes are fabricated and investigated. Systematic tests are carried out to study the influence of different process parameters including the volume of a mother droplet, the dragging velocity, the number of spikes and the dragging directions to the deposition process. The results indicate that creating microarrays by dragging large droplets on patterned hydrophilic-superhydrophobic surfaces yield a reliable, cost-efficient, high-accuracy and easily scalable deposition. The volume of the daughter droplet grows with the velocity of the mother droplet and the number of spikes in a pattern, and decreases with the volume of the mother droplet.

Friction and Wetting Transitions of Magnetic Droplets on Micropillared Superhydrophobic Surfaces.

Reliable characterization of wetting properties is essential for the development and optimization of superhydrophobic surfaces. Here, the dynamics of superhydrophobicity is studied including droplet friction and wetting transitions by using droplet oscillations on micropillared surfaces. Analyzing droplet oscillations by high-speed camera makes it possible to obtain energy dissipation parameters such as contact angle hysteresis force and viscous damping coefficients, which indicate pinning and viscous losses, respectively. It is shown that the dissipative forces increase with increasing solid fraction and magnetic force. For 10 µm diameter pillars, the solid fraction range within which droplet oscillations are possible is between 0.97% and 2.18%. Beyond the upper limit, the oscillations become heavily damped due to high friction force. Below the lower limit, the droplet is no longer supported by the pillar tops and undergoes a Cassie-Wenzel transition. This transition is found to occur at lower pressure for a moving droplet than for a static droplet. The findings can help to optimize micropillared surfaces for low-friction droplet transport.

Oscillating Ferrofluid Droplet Microrheology of Liquid-Immersed Sessile Droplets.

The damped oscillations of liquid-immersed ferrofluid sessile droplets were studied with high-speed imaging experiments and analytical modeling to develop a novel microrheology technique. Droplet oscillations were induced with an external magnetic field, thereby avoiding transients in the resulting vibrational response of the droplet. By following the droplet relaxation with a high-speed camera, the frequency and relaxation time of the damped harmonic oscillations were measured. We extend upon existing analytical theories to describe our liquid-immersed sessile droplet system, and directly quantify the droplet relaxation with the viscosity of the internal and external fluid as well as the interfacial tension between these. The easily controllable magnetic droplets make our oscillating ferrofluid droplet technique a potential candidate for high-throughput microrheology and tensiometry in the future.

Complexes of Magnetic Nanoparticles with Cellulose Nanocrystals as Regenerable, Highly Efficient, and Selective Platform for Protein Separation.

We present an efficient approach to develop cellulose nanocrystal (CNC) hybrids with magnetically responsive Fe3O4 nanoparticles that were synthesized using the (Fe3+/Fe2+) coprecipitation. After 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-catalyzed oxidation of CNC, carbodiimide (EDC/NHS) was used for coupling amine-containing iron oxide nanoparticles that were achieved by dopamine ligand exchange (NH2-Fe3O4 NPs). The as-prepared hybrids (Fe3O4@CNC) were further complexed with Cu(II) ions to produce specific protein binding sites. The performance of magnetically responsive Cu-Fe3O4@CNC hybrids was assessed by selectively separating lysozyme from aqueous media. The hybrid system displayed a remarkable binding capacity with lysozyme of 860.6 ± 14.6 mg/g while near full protein recovery (∼98%) was achieved by simple elution. Moreover, the regeneration of Fe3O4@CNC hybrids and efficient reutilization for protein separation was demonstrated. Finally, lysozyme separation from matrices containing egg white was achieved, thus revealing the specificity and potential of the presented method.

Recognition of Viologen Derivatives in Water by N-Alkyl Ammonium Resorcinarene Chlorides.

Three water-soluble N-alkyl ammonium resorcinarene chlorides decorated with terminal hydroxyl groups at the lower rims were synthesized and characterized. The receptors were decorated at the upper rim with either terminal hydroxyl, rigid cyclohexyl, or flexible benzyl groups. The binding affinities of these receptors toward three viologen derivatives, two of which possess an acetylmethyl group attached to one of the pyridine nitrogens, in water were investigated via 1H NMR spectroscopy, fluorescence spectroscopy, and isothermal titration calorimetry (ITC). ITC quantification of the binding process gave association constants of up to 103 M-1. Analyses reveal a spontaneous binding process which are all exothermic and are both enthalpy and entropy driven.

Micropatterning of silver nanoclusters embedded in polyvinyl alcohol films.

Direct laser writing has been utilized to fabricate highly photostable fluorescent nanocluster microstructures in an organic polymer poly(methacrylic acid), where the carboxyl functional group is reported to play a vital role in nanocluster stabilization. In this Letter, we demonstrate that not only the polymer containing the carboxyl functional group, but also the polymer comprising the hydroxyl group, namely polyvinyl alcohol (PVA), can act as an appropriate stabilizer matrix for laser-induced synthesis and patterning of silver nanoclusters. The as-formed nanoclusters in the PVA film exhibit broadband emission and photostability comparable to the nanoclusters formed in the poly(methacrylic acid) polymer. As PVA is a widely used, nontoxic, biocompatible and biodegradable polymer, the technique of patterning fluorescent nanoclusters in PVA thin films is expected to find numerous applications in fields like fluorescence imaging, biolabeling, and sensing.

N-Alkyl Ammonium Resorcinarene Salts as High-Affinity Tetravalent Chloride Receptors.

N-Alkyl ammonium resorcinarene salts (NARYs, Y=triflate, picrate, nitrate, trifluoroacetates and NARBr) as tetravalent receptors, are shown to have a strong affinity for chlorides. The high affinity for chlorides was confirmed from a multitude of exchange experiments in solution (NMR and UV/Vis), gas phase (mass spectrometry), and solid-state (X-ray crystallography). A new tetra-iodide resorcinarene salt (NARI) was isolated and fully characterized from exchange experiments in the solid-state. Competition experiments with a known monovalent bis-urea receptor (5) with strong affinity for chloride, reveals these receptors to have a much higher affinity for the first two chlorides, a similar affinity as 5 for the third chloride, and lower affinity for the fourth chloride. The receptors affinity toward chloride follows the trend K1 ≫K2 ≫K3 ≈5>K4, with Ka =5011 m(-1) for 5 in 9:1 CDCl3/[D6]DMSO.

Reversible switching between superhydrophobic states on a hierarchically structured surface.

Nature offers exciting examples for functional wetting properties based on superhydrophobicity, such as the self-cleaning surfaces on plant leaves and trapped air on immersed insect surfaces allowing underwater breathing. They inspire biomimetic approaches in science and technology. Superhydrophobicity relies on the Cassie wetting state where air is trapped within the surface topography. Pressure can trigger an irreversible transition from the Cassie state to the Wenzel state with no trapped air--this transition is usually detrimental for nonwetting functionality and is to be avoided. Here we present a new type of reversible, localized and instantaneous transition between two Cassie wetting states, enabled by two-level (dual-scale) topography of a superhydrophobic surface, that allows writing, erasing, rewriting and storing of optically displayed information in plastrons related to different length scales.