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When a drop of a polar liquid slides over a hydrophobic surface, it acquires a charge. As a result, the surface charges oppositely. For applications such as the generation of electric energy, lubricant-infused surfaces (LIS) may be important because they show a low friction for drops. However, slide electrification on LIS has not been studied yet. Here, slide electrification on lubricant-infused surfaces was studied by measuring the charge generated by series of water drops sliding down inclined surfaces. As LIS, we used PDMS-coated glass with micrometer-thick silicone oil films on top. For PDMS-coated glass without lubricant, the charge for the first drop is highest. Then it decreases and saturates at a steady state charge per drop. With lubricant, the drop charge starts from 0, then it increases and reaches a maximum charge per drop. Afterward, it decreases again before reaching its steady-state value. This dependency is not a unique phenomenon for lubricant-infused PDMS; it also occurs on lubricant-infused micropillar surfaces. We attribute this dependency of charge on drop numbers to a change in surface conductivity and depletion of lubricant. These findings are helpful for understanding the charge process and optimizing solid-liquid nanogenerator devices in applications.

Semicrystalline polymers are solids that are supposed to flow only above their melting temperature. By using confinement within nanoscopic cylindrical pores, we show that a semicrystalline polymer can flow at temperatures below the melting point with a viscosity intermediate to the melt and crystal states. During this process, the capillary force is strong and drags the polymer chains in the pores without melting the crystal. The unexpected enhancement in flow, while preserving the polymer crystallites, is of importance in the design of polymer processing conditions applicable at low temperatures, e.g., cold drawn polymers such as polytetrafluoroethylene, self-healing, and in nanoconfined donor/acceptor polymers used in organic electronics.

Polymers conjugated with active agents have applications in biomedicine, anticorrosion, and smart agriculture. When the active agent is used as a drug, corrosion inhibitor, or pesticide, it can be released upon a specific stimulus. The efficiency and the sustainability of active agents are determined by the released kinetics. In this work, we study the fast-release kinetics of 8-hydroxyquinoline (8HQ) from a pH-responsive, random copolymer of methyl methacrylate and 8-quinolinyl-sulfide-ethyl acrylate [P(MMA- co-HQSEA)] by hydrolysis of the β-thiopropionate groups. We used contact angle measurements of sliding drops as an elegant way to characterize the release kinetics. Based on the results gained from 1H nuclear magnetic resonance measurement, fluorescent intensity measurement, and velocity-dependent contact angle measurement, we found that both the hydrolysis rate and polymer conformation affect the release kinetics of 8HQ from a P(MMA- co-HQSEA) film. Polymer chains collapse and further suppress the release from the inner layer in acidic conditions, while polymer chains in a stretched condition further facilitate the release from the inner layer. As a result, the cumulative release rate of 8HQ is higher in the basic condition than in the acidic condition.

Water drops moving on surfaces are not only an everyday phenomenon seen on windows but also form an essential part of many industrial processes. Previous understanding is that drop motion is dictated by viscous dissipation and activated dynamics at the contact line. Here we demonstrate that these two effects cannot fully explain the complex paths of sliding or impacting drops. To accurately determine the forces experienced by moving drops, we imaged their trajectory when sliding down a tilted surface, and applied the relevant equations of motion. We found that drop motion on low-permittivity substrates is substantially influenced by electrostatic forces. Our findings confirm that electrostatics must be taken into consideration for the description of the motion of water, aqueous electrolytes and ethylene glycol on hydrophobic surfaces. Our results are relevant for improving the control of drop motion in many applications, including printing, microfluidics, water management and triboelectric nanogenerators.

The use of nanoparticles as carriers to deliver pharmacologically active compounds to specific parts of the body via the bloodstream is a promising therapeutic approach for the effective treatment of various diseases. To reach their target sites, nanocarriers (NCs) need to circulate in the bloodstream for prolonged periods without aggregation, degradation, or cargo loss. However, it is very difficult to identify and monitor small-sized NCs and their cargo in the dense and highly complex blood environment. Here, we present a new fluorescence correlation spectroscopy-based method that allows the precise characterization of fluorescently labeled NCs in samples of less than 50 μL of whole blood. The NC size, concentration, and loading efficiency can be measured to evaluate circulation times, stability, or premature drug release. We apply the new method to follow the fate of pH-degradable fluorescent cargo-loaded nanogels in the blood of live mice for periods of up to 72 h.

Superhydrophobic nanostructured surfaces can enhance water condensation efficiency by facilitating droplet departure via coalescence-induced jumping. However, condensed droplets tend to transit from a mobile jumping mode to a highly pinned state at high condensation heat flux because excessive water nucleates within the nanostructures and anchors the condensed droplets. The large pinned droplets act as a thermal barrier and insulate the cooling surface, thus severely degrading its heat transfer efficiency. This work developed a nanohierarchical structured surface by growing branched TiO₂ nanorod arrays to prevent condensation-induced droplet pinning. After hydrophobization, the nano-hierarchical structure can spontaneously push the water out of nanostructures with an outward Laplace capillary pressure gradient when the droplet size is only at the nanoscale level. This effective de-wetting process maintains the high droplet mobility on the nano-hierarchical surface over a wide subcooling range, resulting in an up to ~ 90 % increase in heat transfer coefficient at a high heat flux of 132 kW•m⁻² compared to the single-tier nanorod surface. Our investigation of how the nanohierarchical structures fundamentally suppress the condensation-induced wetting on superhydrophobic surfaces represents a significant advance in understanding multiphase wetting phenomena and paves the way for the rational design of cooling surfaces. ISSN:0300-9467 ISSN:1385-8947 ISSN:1873-3212 ISSN:0923-0467

When a particle, such as dust, contacts a thin liquid film covering a surface it is trapped by the liquid. This effect is caused by the formation of a meniscus, resulting in a capillary force that makes the particle adhere to the surface. While capillary adhesion is well-characterised in static situations, the dynamic formation of the liquid bridge after the initial contact is highly intricate. Here, we experimentally study the evolution of a liquid bridge after a glass sphere is gently brought into contact with a thin viscous film. It is found that the contact creates a ripple on the thin film, which influences the growth of the meniscus. Initially, the ripple and the meniscus are coupled and exhibit similar dynamics. This initial regime is well accounted for by a scaling law derived from lubrication theory. At a later stage, the ripple is “detached” from the liquid bridge, leading to a second regime of bridge dynamics. As a result, capillary forces are time-dependent, highlighting the importance of dynamics on adhesion.

In this work, 1,2,4,5-benzenetetracarboxylic acid (BT) is used as a cross-linker to improve the oxidative thermostabilization of lignin-rich nanofibers so that the activated carbon nanofiber (ACNF)...

Wetting imperfections are omnipresent on surfaces. They cause contact angle hysteresis and determine the wetting dynamics. Still, existing techniques (e.g., contact angle goniometry) are not sufficient to localize inhomogeneities and image wetting variations. We overcome these limitations through scanning drop friction force microscopy (sDoFFI). In sDoFFI, a 15 μL drop of Milli-Q water is raster-scanned over a surface. The friction force (lateral adhesion force) acting on the moving contact line is plotted against the drop position. Using sDoFFI, we obtained 2D wetting maps of the samples having sizes in the order of several square centimeters. We mapped areas with distinct wetting properties such as those present on a natural surface (e.g., a rose petal), a technically relevant superhydrophobic surface (e.g., Glaco paint), and an in-house prepared model of inhomogeneous surfaces featuring defined areas with low and high contact angle hysteresis. sDoFFI detects features that are smaller than 0.5 mm in size. Furthermore, we quantified the sliding behavior of drops across the boundary separating areas with different contact angles on the model sample. The sliding of a drop across this transition line follows a characteristic stick-slip motion. We use the variation in force signals, advancing and receding contact line velocities, and advancing and receding contact angles to identify zones of stick and slip. When scanning the drop from low to high contact angle hysteresis, the drop undergoes a stick-slip-stick-slip motion at the interline. Sliding from high to low contact angle hysteresis is characterized by the slip-stick-slip motion. The sDoFFI is a new tool for 2D characterization of wetting properties, which is applicable to laboratory-based samples but also characterizes biological and commercial surfaces.

The charge state of dielectric surfaces in aqueous environments is of fundamental and technological importance. Here, we study the influence of dissolved molecular CO

The attachment of bio-fluids to surfaces promotes the transmission of diseases. Superhydrophobic textiles may offer significant advantages for reducing the adhesion of bio-fluids. However, they have not yet found widespread use because dried remnants adhere strongly and have poor mechanical or chemical robustness. In addition, with the massive use of polymer textiles, features such as fire and heat resistance can reduce the injuries and losses suffered by people in a fire accident. We developed a superhydrophobic textile covered with a hybrid coating of titanium dioxide and polydimethylsiloxane (TiO

Metallodrugs are widely used in cancer treatment. The modification of metallodrugs with polyethylene glycol (PEGylation) prolongs blood circulation and improves drug accumulation in tumors; it represents a general strategy for drug delivery. However, PEGylation hinders cellular internalization and tumor penetration, which reduce therapeutic efficacy. Herein, the red-light-enhanced cellular internalization and tumor penetration of a PEGylated anticancer agent, PEGylated Ru complex (Ru-PEG), are reported upon. Ru-PEG contains a red-light-cleavable PEG ligand, anticancer Ru complex moiety, and fluorescent pyrene group for imaging and self-assembly. Ru-PEG self-assembles into vesicles that circulate in the bloodstream and accumulate in the tumors. Red-light irradiation induces dePEGylation and changes the Ru-PEG vesicles to large compound micelles with smaller diameters and higher zeta potentials, which enhance tumor penetration and cellular internalization. Red-light irradiation also generates intracellular

Photodynamic bonds are stable in the dark and can reversibly dissociate/form under light irradiation. Photodynamic bonds are promising building blocks for responsive or healable materials, photoactivated drugs, nanocarriers, extracellular matrices, etc. However, reactive intermediates from photodynamic bonds usually lead to side reactions, which limit the use of photodynamic bonds. Here, we report that the Ru-Se coordination bond is a new photodynamic bond that reversibly dissociates under mild visible-light-irradiation conditions. We observed that Ru-Se bonds form via the coordination of a selenoether ligand with [Ru(tpy)(biq)(H2O)]Cl2 (tpy = 2,2':6',2″-terpyridine, biq = 2,2'-biquinoline) in the dark, while the Ru-Se bond reversibly dissociates under visible-light irradiation. No side reaction is detected in the formation and dissociation of Ru-Se bonds. To demonstrate that the Ru-Se bond is applicable to different operating environments, we prepared photoresponsive amphiphiles, surfaces, and polymer gels using Ru-Se bonds. The amphiphiles with Ru-Se bonds showed reversible morphological transitions between spherical micelles and bowl-shaped assemblies for dark/light irradiation cycles. The surfaces modified with Ru-Se-bond-containing compounds showed photoswitchable wettability. Polymer gels with Ru-Se cross-links underwent photoinduced reversible sol-gel transitions, which can be used for reshaping and healing. Our work demonstrates that the Ru-Se bond is a new type of dynamic bond, which can be used for constructing responsive, reprocessable, switchable, and healable materials that work in a variety of environments.

The control of liquid motion on the micrometer scale is important for many liquid transport and biomedical applications. An efficient way to trigger liquid motion is by introducing surface tension gradients on free liquid interfaces leading to the Marangoni effect. However, a pronounced Marangoni-driven flow generally only occurs at a liquid–air or liquid–liquid interface but not at solid–liquid interfaces. Using superhydrophobic surfaces, the liquid phase stays in the Cassie state (where liquid is only in contact with the tips of the rough surface structure and air is enclosed in the indentations of the roughness) and hence provides the necessary liquid–air interface to trigger evident Marangoni flows. We use light to asymmetrically heat this interface and thereby control liquid motion near superhydrophobic surfaces. By laser scanning confocal microscopy, we determine the velocity distribution evolving through optical excitation. We show that Marangoni flow can be induced optically at structured, air-entrapping superhydrophobic surfaces. Furthermore, by comparison with numerical modeling, we demonstrate that in addition to the Marangoni flow, buoyancy-driven flow occurs. This effect has so far been neglected in similar approaches and models of thermocapillary driven flow at superhydrophobic surfaces. Our work yields insight into the physics of Marangoni flow and can help in designing new contactless, light-driven liquid transport systems, e.g., for liquid pumping or in microfluidic devices.

We present an experimental approach to studying the kinetics of polymer nanoparticle formation using molecular rotor molecules as fluorescence probes. By combining fluorescence lifetime analysis and fluorescence correlation spectroscopy, it is possible to simultaneously monitor the evolution of the local environment in the nanoparticles and their size. To assess the generality of the method, we select two common but very different methods for nanoparticle preparation: emulsion-solvent evaporation and miniemulsion polymerization. In both cases, three stages of the nanoparticle formation process were identified on the basis of their polymer content. In the initial stage of the process, the polymer content is low. Then it increases rapidly because of solvent evaporation or polymerization during the second stage. Finally, it reaches a plateau value. Furthermore, significant heterogeneities in the final nanoparticles were found that can be attributed to remaining solvent or monomer and the spatial variation of the polymer-free volume.

Solid surfaces, in particular polymer surfaces, are able to adapt upon contact with a liquid. Adaptation results in an increase in contact angle hysteresis and influences the mobility of sliding drops on surfaces. To study adaptation and its kinetics, we synthesized a random copolymer composed of styrene and 11–25 mol% acrylic acid (PS/PAA). We measured the dynamic advancing (θA) and receding (θR) contact angles of water drops sliding down a tilted plate coated with this polymer. We measured θA ≈ 87° for velocities of the contact line

It is challenging to treat multidrug-resistant tumors because such tumors are resistant to a broad spectrum of structurally and functionally unrelated drugs. Herein, treatment of multidrug-resistant tumors using red-light-responsive metallopolymer nanocarriers that are conjugated with the anticancer drug chlorambucil (CHL) and encapsulated with the anticancer drug doxorubicin (DOX) is reported. An amphiphilic metallopolymer PolyRuCHL that contains a poly(ethylene glycol) (PEG) block and a red-light-responsive ruthenium (Ru)-containing block is synthesized. Chlorambucil is covalently conjugated to the Ru moieties of PolyRuCHL. Encapsulation of DOX into PolyRuCHL in an aqueous solution results in DOX@PolyRuCHL micelles. The DOX@PolyRuCHL micelles are efficiently taken up by the multidrug-resistant breast cancer cell line MCF-7R and which carries DOX into the cells. Free DOX, without the nanocarriers, is not taken up by MCF-7R or pumped out of MCF-7R via P-glycoproteins. Red light irradiation of DOX@PolyRuCHL micelles triggers the release of chlorambucil-conjugated Ru moieties and DOX. Both act synergistically to inhibit the growth of multidrug-resistant cancer cells. Furthermore, the inhibition of the growth of multidrug-resistant tumors in a mouse model using DOX@PolyRuCHL micelles is demonstrated. The design of red-light-responsive metallopolymer nanocarriers with both conjugated and encapsulated drugs opens up an avenue for photoactivated chemotherapy against multidrug-resistant tumors.

This manuscript is dedicated to honour our dear colleague and friend Peter Kralchevsky.

The development of switchable adhesives for reversible bonding and debonding can overcome the problems associated with conventional adhesives in separating, recycling, and repairing glued surfaces. Here, a photoresponsive azobenzene-containing polymer (azopolymer) is developed for photocontrolled adhesion. The azopolymer P1 (poly(6-(4-(p-tolyldiazenyl)phenoxy)hexyl acrylate)) exhibits photoinduced reversible solid-to-liquid transitions due to trans–cis photoisomerization. Trans P1 is a solid that glues two substrates with a stiffness comparable to that of conventional adhesives. UV light induces trans-to-cis isomerization, liquefies P1, weakens the adhesion, and facilitates the separation of glued substrates. Conversely, visible light induces cis-to-trans isomerization, solidifies P1, and enhances the adhesion. P1 enables photocontrolled reversible adhesion for various substrates with different wettability, chemical compositions, and surface roughness. P1 can also be implemented in both dry and wet enviro...

Mechanical robustness and healing ability are important properties of polymeric materials. However, the development of mechanically robust yet rapidly healable polymers is challenging. Herein, we d...

Resolving the long-standing problem of hydrate plugging in oil and gas pipelines has driven an intense quest for mechanisms behind the plug formation. However, existing theories of hydrate agglomeration have critical shortcomings, for example, they cannot describe nanometer-range capillary forces at hydrate surfaces that were recently observed by experiments. Here, we present a new model for hydrate agglomeration which includes premelting of hydrate surfaces. We treat the premelting layer on hydrate surfaces such as a thin liquid film on a substrate and propose a soft-sphere model of hydrate interactions. The new model describes the premelting-induced capillary force between a hydrate surface and a pipe wall or another hydrate. The calculated adhesive force between 0, degree a hydrate sphere (R = 300 mu m) and a solid surface varies from 0.3 mN on a hydrophilic surface (contact angle, theta = 0 degrees) to 0.008 mN on a superhydrophobic surface (theta = 160 degrees). The initial contact area is 4 orders of magnitude smaller than the cross-sectional area of the hydrate sphere and can expand with increasing contact time because of the consolidation of hydrate particles on the solid surface. Our model agrees with the available experimental results and can serve as a conceptual guidance for developing a chemical-free environmentally friendly method for prevention of hydrate plugs via surface coating of pipe surfaces.