Deposition of high‐speed droplets on inverted surfaces is important to many fundamental scientific principles and technological applications. For example, in pesticide spraying to target pests and diseases emerging on abaxial side of leaves, the downward rebound and gravity of the droplets make the deposition exceedingly difficult on hydrophobic/superhydrophobic leaf underside, causing serious pesticide waste and environmental pollution. Here, a series of bile salt/cationic surfactant coacervates are developed to attain efficient deposition on the inverted surfaces of diverse hydrophobic/superhydrophobic characteristics. The coacervates have abundant nanoscale hydrophilic/hydrophobic domains and intrinsic network‐like microstructures, which endow them with efficient encapsulation of various solutes and strong adhesion to surface micro/nanostructures. Thus, the coacervates with low viscosity achieve high‐efficient deposition on superhydrophobic abaxial‐side of tomato leaves and inverted artificial surfaces with a water contact angle from 170° to 124°, much better than that of commercial agricultural adjuvants. Intriguingly, the compactness of network‐like structures dominantly controls adhesion force and deposition efficiency, and the most crowded one leads to the most efficient deposition. The tunable coacervates can help comprehensively understand the complex dynamic deposition, and provide innovative carriers for depositing sprayed pesticides on abaxial and adaxial sides of leaves, thereby potentially reducing pesticide use and promoting sustainable agriculture.

Osteoarthritic joints contain lower molecular weight (MW) hyaluronan (hyaluronic acid, HA) than healthy joints. To understand the relevance of this HA-size effect for joint lubrication, the friction and surface structure of cartilage-emulating surfaces with HA of different MW were studied using a surface force balance (SFB), and atomic force microscopy (AFM) . Gelatin (gel)-covered mica surfaces were coated with either high MW HA (HHA), medium MW HA (MHA) or low MW HA (LHA), and lipids of Hydrogenated Soy L-α-phosphatidylcholine (HSPC) in the form of small unilamellar vesicles, using a layer-by-layer assembly method. SFB results indicate that the gel-HHA-HSPC boundary layer provides very efficient lubrication, attributed to hydration lubrication at the phosphocholine head-groups exposed by the HA-attached lipids, with friction coefficients (COF) as low as l0-3–10-4 at contact stresses at least up to P = 120 atm. However, for the gel-MHA-HSPC and gel-LHA-HSPC surfaces, the friction, initially low, increases sharply at much lower pressures (up to 30–60 atm at most). This higher friction with the shorter chains may be due to their weaker total adhesion energy to the gelatin, where the attraction between the negatively-charged HA and the weakly-positively charged gelatin is attributed largely to counterion-release entropy. Thus the complexes of LHA and MHA with the lubricating HSPC lipids are more easily removed by shear during sliding, especially at high stresses, than is the HHA-HSPC complex which is strongly adhered to the gelatin. This is ultimately the reason for lower-pressure lubrication breakdown with the shorter polysaccharides. Our results provide molecular level insight into why the decrease in HA molecular weight in osteoarthritic joints may be associated with higher friction at the articular cartilage surface, and may have relevance for treatments of osteoarthritis involving intra-articular HA injections.

This work studied gemini-like surfactants formed from anionic surfactant sodium dodecyl sulfate (SDS) and cationic charged bola-type diamines with hydrophilic or hydrophobic spacers of different lengths using surface tension, small angle neutron scattering, isothermal titration microcalorimetry and cryogenic transmission electron microscopy. The critical micelle concentrations (CMC) and the surface tension at CMC (γ_CMC) for all the diamine/SDS mixtures are markedly lower than that of SDS. The shorter diamines reduce γ_CMC to a greater extent regardless of the hydrophilicity/hydrophobicity of the diamines. Meanwhile, either the hydrophobic diamine with a longer spacer or the hydrophilic diamine with a shorter spacer is more beneficial to decrease CMC and leads to the transition from spherical micelles into rodlike or wormlike micelles. This is principally because of the formation of gemini-like surfactants by the electrostatic binding between SDS and the diamines, where the electrostatic repulsion between the adjacent headgroups of SDS becomes much weaker due to the electrostatic binding of oppositely charged diamine with SDS, and the longer hydrophobic spacer may also bend into the hydrophobic domain of micelles to promote micellar growth. However, the hydrophilic spacers are more compatible with the headgroup region, leading to micelles with a larger curvature. This work contributes to the understanding of the relationship between the properties of constructed gemini-like surfactants and the natures of connecting molecules, and provides guidance to efficiently improve the performance of surfactants.