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.

Droplet Friction on Superhydrophobic Surfaces Scales With Liquid-Solid Contact Fraction.

It is generally assumed that contact angle hysteresis of superhydrophobic surfaces scales with liquid-solid contact fraction, however, its experimental verification has been problematic due to the limited accuracy of contact angle and sliding angle goniometry. Advances in cantilever-based friction probes enable accurate droplet friction measurements down to the nanonewton regime, thus suiting much better for characterizing the wetting of superhydrophobic surfaces than contact angle hysteresis measurements. This work quantifies the relationship between droplet friction and liquid-solid contact fraction, through theory and experimental validation. Well-defined micropillar and microcone structures are used as model surfaces to provide a wide range of different liquid-solid contact fractions. Micropillars are known to be able to hold the water on top of them, and a theoretical analysis together with confocal laser scanning microscopy shows that despite the spiky nature of the microcones droplets do not sink into the conical structure either, rendering a diminishingly small liquid-solid contact fraction. Droplet friction characterization with a micropipette force sensor technique reveals a strong dependence of the droplet friction on the contact fraction, and the dependency is described with a simple physical equation, despite the nearly three-orders-of-magnitude difference in liquid-solid contact fraction between the sparsest cone surface and the densest pillar surface.

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.

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.

Partitioning of caffeine in lipid bilayers reduces membrane fluidity and increases membrane thickness.

Caffeine is a small amphiphilic molecule, which is widely consumed as a stimulant to prevent fatigue, but is also used as a common drug adjuvant in modern medicine. Here, we show that caffeine interacts with unsaturated lipid membranes made of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC). By combining X-ray diffraction and molecular dynamics simulations, we present evidence that caffeine partitions in lipid membranes and locates at the head group-tail group interface of the bilayers. By attracting water molecules from neighboring lipid molecules, it leads to the formation of "water pockets", i.e., a local increase of water density at this interface. Through this mechanism, caffeine leads to an overall decrease of the gauche defect density in the membranes and an increase of membrane thickness, indicating a loss of membrane fluidity. These non-specific membrane interactions may increase the efficacy of analgesic drugs through changes in the bioavailability and rate of metabolism of these drugs.

Cross-Linked Hydrogels Formed through Diels-Alder Coupling of Furan- and Maleimide-Modified Poly(methyl vinyl ether-alt-maleic acid).

The Diels-Alder [4 + 2] cycloaddition between furan- and maleimide-functional polyanions was used to form cross-linked synthetic polymer hydrogels. Poly(methyl vinyl ether-alt-maleic anhydride) was reacted with furfurylamine or N-(2-aminoethyl)maleimide in acetonitrile to form pairs of furan- and maleimide-functionalized poly(methyl vinyl ether-alt-maleic acid)s. Mixtures of these mutually reactive polyanions in water gelled within 15 min to 18 h, depending on degree of functionalization and polymer concentrations. Solution and magic-angle spinning (1)H NMR were used to confirm the formation of the Diels-Alder adduct, to analyze competing hydrolytic side reactions, and demonstrate postgelation functionalization. The effect of the degree of furan and maleimide functionalization, polymer concentration, pH, and calcium ion concentration, on gelation time, gel mechanical properties, and equilibrium swelling, are described. Release of dextran as a model drug was studied using fluorescence spectroscopy, as a function of gel composition and calcium treatment.

Amyloid-ß(25-35) peptides aggregate into cross-ß sheets in unsaturated anionic lipid membranes at high peptide concentrations.

One of the hallmarks of Alzheimer's disease is the formation of protein plaques in the brain, which mainly consist of amyloid-ß peptides of different lengths. While the role of these plaques in the pathology of the disease is not clear, the mechanism behind peptide aggregation is a topic of intense research and discussion. Because of their simplicity, synthetic membranes are promising model systems to identify the elementary processes involved. We prepared unsaturated zwitterionic/anionic lipid membranes made of 1-palmitoyl-2-oleoyl-sn-glycero-phosphocholine (POPC) and 1,2-dimyristoyl-sn-glycero-3-phospho-l-serine (DMPS) at concentrations of POPC/3 mol% DMPS containing 0 mol%, 3 mol%, 10 mol%, and 20 mol% amyloid-ß25-35 peptides. Membrane-embedded peptide clusters were observed at peptide concentrations of 10 and 20 mol% with a typical cluster size of ∼11 µm. Cluster density increased with peptide concentration from 59 (±3) clusters per mm(2) to 920 (±64) clusters per mm(2), respectively. While monomeric peptides take an α-helical state when embedded in lipid bilayers at low peptide concentrations, the peptides in peptide clusters were found to form cross-ß sheets and showed the characteristic pattern in X-ray experiments. The presence of the peptides was accompanied by an elastic distortion of the bilayers, which can induce a long range interaction between the peptides. The experimentally observed cluster patterns agree well with Monte Carlo simulations of long-range interacting peptides. This interaction may be the fundamental process behind cross-ß sheet formation in membranes and these sheets may serve as seeds for further growth into amyloid fibrils.

Viscoelastic properties of the nematode Caenorhabditis elegans, a self-similar, shear-thinning worm.

Undulatory motion is common to many creatures across many scales, from sperm to snakes. These organisms must push off against their external environment, such as a viscous medium, grains of sand, or a high-friction surface; additionally they must work to bend their own body. A full understanding of undulatory motion, and locomotion in general, requires the characterization of the material properties of the animal itself. The material properties of the model organism Caenorhabditis elegans were studied with a micromechanical experiment used to carry out a three-point bending measurement of the worm. Worms at various developmental stages (including dauer) were measured and different positions along the worm were probed. From these experiments we calculated the viscoelastic properties of the worm, including the effective spring constant and damping coefficient of bending. C. elegans moves by propagating sinusoidal waves along its body. Whereas previous viscoelastic approaches to describe the undulatory motion have used a Kelvin-Voigt model, where the elastic and viscous components are connected in parallel, our measurements show that the Maxwell model, where the elastic and viscous components are in series, is more appropriate. The viscous component of the worm was shown to be consistent with a non-Newtonian, shear-thinning fluid. We find that as the worm matures it is well described as a self-similar elastic object with a shear-thinning damping term and a stiffness that becomes smaller as one approaches the tail.

The nematode C. elegans as a complex viscoelastic fluid.

The viscoelastic material properties of the model organism C. elegans were probed with a micropipette deflection technique and modelled with the standard linear solid model. Dynamic relaxation measurements were performed on the millimetric nematode to investigate its viscous characteristics in detail. We show that the internal properties of C. elegans can not be fully described by a simple Newtonian fluid. Instead, a power-law fluid model was implemented and shown to be in excellent agreement with experimental results. The nematode exhibits shear thinning properties and its complex fluid characteristics were quantified. The bending-rate dependence of the internal damping coefficient of C. elegans could affect its gait modulation in different external environments.

Direct measurements of drag forces in C. elegans crawling locomotion.

With a simple and versatile microcantilever-based force measurement technique, we have probed the drag forces involved in Caenorhabditis elegans locomotion. As a worm crawls on an agar surface, we found that substrate viscoelasticity introduces nonlinearities in the force-velocity relationships, yielding nonconstant drag coefficients that are not captured by original resistive force theory. A major contributing factor to these nonlinearities is the formation of a shallow groove on the agar surface. We measured both the adhesion forces that cause the worm's body to settle into the agar and the resulting dynamics of groove formation. Furthermore, we quantified the locomotive forces produced by C. elegans undulatory motions on a wet viscoelastic agar surface. We show that an extension of resistive force theory is able to use the dynamics of a nematode's body shape along with the measured drag coefficients to predict the forces generated by a crawling nematode.

Tangling of tethered swimmers: interactions between two nematodes.

The tangling of two tethered microswimming worms serving as the ends of "active strings" is investigated experimentally and modeled analytically. C. elegans nematodes of similar size are caught by their tails using micropipettes and left to swim and interact at different separations over long times. The worms are found to tangle in a reproducible and statistically predictable manner, which is modeled based on the relative motion of the worm heads. Our results provide insight into the intricate tangling interactions present in active biological systems.

Capillary levelling of a cylindrical hole in a viscous film.

The capillary levelling of cylindrical holes in viscous polystyrene films was studied using atomic force microscopy as well as quantitative analytical scaling arguments based on thin film theory and self-similarity. The relaxation of the holes was shown to consist of two different time regimes: an early regime where opposing sides of the hole do not interact, and a late regime where the hole is filling up. For the latter, the self-similar asymptotic profile was derived analytically and shown to be in excellent agreement with experimental data. Finally, a binary system of two holes in close proximity was investigated where the individual holes fill up at early times and coalesce at longer times.

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.

Roughness of glancing angle deposited titanium thin films: an experimental and computational study.

The characterization of roughness at the nanoscale by the means of atomic force microscopy (AFM) was performed on high aspect ratio glancing angle deposited titanium thin films. With the use of scanning electron microscopy as well as x-ray photoelectron spectroscopy, it was shown that the AFM measurements gave rise to incorrect roughness values for the films consisting of the highest aspect ratio structures. By correcting for this experimental artefact, the difference between the saturated roughness value of a film grown with conventional physical vapour deposition and films grown with a glancing angle of deposition was shown to behave as a power law function of the deposition angle, with a saturated roughness exponent of κ = 7.1 ± 0.2. This power law scaling was confirmed by three-dimensional molecular dynamics simulations of glancing angle deposition, where the saturated roughness exponent was calculated to κ = 6.7 ± 0.4.

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.

Viscosity-enhanced droplet motion in sealed superhydrophobic capillaries.

It is well known that an increased viscosity slows down fluid dynamics. Here we show that this intuitive rule is not general and can fail for liquids flowing in confined liquid-repellent systems. A gravity-driven, highly viscous glycerol droplet inside a sealed superhydrophobic capillary is moving more than 10 times faster than a water droplet with three-orders-of-magnitude lower viscosity. Using tracer particles, we show that the low-viscosity droplets are rapidly rotating internally, with flow velocities greatly exceeding the center-of-mass velocity. This is in stark contrast to the faster moving high-viscosity droplets with nearly vanishing internal flows. The anomalous viscosity-enhanced flow is caused by a viscosity-suppressed deformation of the droplet-air interface and a hydro- and aerodynamic coupling between the droplet and the air trapped within the micro/nanostructures (plastron). Our work demonstrates the unexpected role of the plastron in controlling fluid flow beyond the mere reduction in contact area and friction.

Ferrofluid Microdroplet Splitting for Population-Based Microfluidics and Interfacial Tensiometry.

Ferrofluids exhibit a unique combination of liquid properties and strong magnetic response, which leads to a rich variety of interesting functional properties. Here, the magnetic-field-induced splitting of ferrofluid droplets immersed in an immiscible liquid is presented, and related fascinating dynamics and applications are discussed. A magnetic field created by a permanent magnet induces instability on a mother droplet, which divides into two daughter droplets in less than 0.1 s. During the splitting process, the droplet undergoes a Plateau-Rayleigh-like instability, which is investigated using high-speed imaging. The dynamics of the resulting satellite droplet formation is shown to depend on the roughness of the supporting surface. Further increasing the field results in additional splitting events and self-assembly of microdroplet populations, which can be magnetically actuated. The effects of magnetization and interfacial tension are systematically investigated by varying magnetic nanoparticles and surfactant concentrations, and a variety of outcomes from labyrinthine patterns to discrete droplets are observed. As the splitting process depends on interfacial tension, the droplet splitting can be used as a measure for interfacial tension as low as 0.1 mN m-1. Finally, a population-based digital microfluidics concept based on the self-assembled microdroplets is presented.

Micropipette force sensors for in vivo force measurements on single cells and multicellular microorganisms.

Measuring forces from the piconewton to millinewton range is of great importance for the study of living systems from a biophysical perspective. The use of flexible micropipettes as highly sensitive force probes has become established in the biophysical community, advancing our understanding of cellular processes and microbial behavior. The micropipette force sensor (MFS) technique relies on measurement of the forces acting on a force-calibrated, hollow glass micropipette by optically detecting its deflections. The MFS technique covers a wide micro- and mesoscopic regime of detectable forces (tens of piconewtons to millinewtons) and sample sizes (micrometers to millimeters), does not require gluing of the sample to the cantilever, and allows simultaneous optical imaging of the sample throughout the experiment. Here, we provide a detailed protocol describing how to manufacture and calibrate the micropipettes, as well as how to successfully design, perform, and troubleshoot MFS experiments. We exemplify our approach using the model nematode Caenorhabditis elegans, but by following this protocol, a wide variety of living samples, ranging from single cells to multicellular aggregates and millimeter-sized organisms, can be studied in vivo, with a force resolution as low as 10 pN. A skilled (under)graduate student can master the technique in ~1-2 months. The whole protocol takes ~1-2 d to finish.

Designed inorganic porous nanovector with controlled release and MRI features for safe administration of doxorubicin.

The inability of traditional chemotherapeutics to reach cancer tissue reduces the treatment efficacy and leads to adverse effects. A multifunctional nanovector was developed consisting of porous silicon, superparamagnetic iron oxide, calcium carbonate, doxorubicin and polyethylene glycol. The particles integrate magnetic properties with the capacity to retain drug molecules inside the pore matrix at neutral pH to facilitate drug delivery to tumor tissues. The MRI applicability and pH controlled drug release were examined in vitro together with in-depth material characterization. The in vivo biodistribution and compound safety were verified using A549 lung cancer bearing mice before proceeding to therapeutic experiments using CT26 cancer implanted mice. Loading doxorubicin into the porous nanoparticle negated the adverse side effects encountered after intravenous administration highlighting the particles' excellent biocompatibility. Furthermore, the multifunctional nanovector induced 77% tumor reduction after intratumoral injection. The anti-tumor effect was comparable with that of free doxorubicin but with significantly alleviated unwanted effects. These results demonstrate that the developed porous silicon-based nanoparticles represent promising multifunctional drug delivery vectors for cancer monitoring and therapy.