Observation of Brownian elastohydrodynamic forces acting on confined soft colloids.

Confined motions in complex environments are ubiquitous in microbiology. These situations invariably involve the intricate coupling between fluid flow, soft boundaries, surface forces, and fluctuations. In the present study, such a coupling is investigated using a method combining holographic microscopy and advanced statistical inference. Specifically, the Brownian motion of soft micrometric oil droplets near rigid walls is quantitatively analyzed. All the key statistical observables are reconstructed with high precision, allowing for nanoscale resolution of local mobilities and femtonewton inference of conservative or nonconservative forces. Strikingly, the analysis reveals the existence of a novel, transient, but large, soft Brownian force. The latter might be of crucial importance for microbiological and nanophysical transport, target finding, or chemical reactions in crowded environments, and hence the whole life machinery.

Evaporation of alcohol droplets on surfaces in moist air.

Droplets of alcohol-based formulations are common in applications from sanitizing sprays to printing inks. However, our understanding of the drying dynamics of these droplets on surfaces and the influence of ambient humidity is still very limited. Here, we report the drying dynamics of picoliter droplets of isopropyl alcohol deposited on a surface under controlled humidity. Condensation of water vapor in the ambient environment onto alcohol droplets leads to unexpectedly complex drying behavior. As relative humidity (RH) increases, we observed a variety of phenomena including enhanced spreading, nonmonotonic changes in the drying time, the formation of pancake-like shapes that suppress the coffee-ring effect, and the formation of water-rich films around an alcohol-rich drop. We developed a lubrication model that accounts for the coupling between the flow field within the drop, the shape of the drop, and the vapor concentration field. The model reproduces many of the experimentally observed morphological and dynamic features, revealing the presence of unusually large spatial compositional gradients within the evaporating droplet and surface-tension-gradient-driven flows arising from water condensation/evaporation at the surface of the droplet. One unexpected feature from the simulation is that water can evaporate and condense concurrently in different parts of the drop, providing fundamental insights that simpler models based on average fluxes lack. We further observed rim instabilities at higher RH that are well-described by a model based on the Rayleigh-Plateau instability. Our findings have implications for the testing and use of alcohol-based disinfectant sprays and printing inks.

Ice friction at the nanoscale.

The origin of ice slipperiness has been a matter of great controversy for more than a century, but an atomistic understanding of ice friction is still lacking. Here, we perform computer simulations of an atomically smooth substrate sliding on ice. In a large temperature range between 230 and 266 K, hydrophobic sliders exhibit a premelting layer similar to that found at the ice/air interface. On the contrary, hydrophilic sliders show larger premelting and a strong increase of the first adsorption layer. The nonequilibrium simulations show that premelting films of barely one-nanometer thickness are sufficient to provide a lubricating quasi-liquid layer with rheological properties similar to bulk undercooled water. Upon shearing, the films display a pattern consistent with lubricating Couette flow, but the boundary conditions at the wall vary strongly with the substrate's interactions. Hydrophobic walls exhibit large slip, while hydrophilic walls obey stick boundary conditions with small negative slip. By compressing ice above atmospheric pressure, the lubricating layer grows continuously, and the rheological properties approach bulk-like behavior. Below 260 K, the equilibrium premelting films decrease significantly. However, a very large slip persists on the hydrophobic walls, while the increased friction on hydrophilic walls is sufficient to melt ice and create a lubrication layer in a few nanoseconds. Our results show that the atomic-scale frictional behavior of ice is a combination of spontaneous premelting, pressure melting, and frictional heating.

Disparate External Electric Field Effect on the Adsorption and Shear Behavior of Monovalent and Trivalent Ions in Electrolyte Solution.

Reducing friction is of great interest, and an external potential applied to the friction pair can regulate lubricity. Electrochemical atomic force microscopy (EC-AFM) is used to study the tribological and adsorption behavior of monovalent and trivalent ionic solutions between charged surfaces. An opposite trend of coefficient of friction (COF) and normal force that varies with the applied electric potential is witnessed. Direct force measurements and theoretical models have disclosed that, for the NaCl solution, the negative electric field reduces the COF by increasing cation adsorption. As for LaCl3 solution, the positive electric field promotes the primary adsorption of anions on HOPG, resulting in the disappearance of the attractive ion-ion correlation between the trivalent ions, thereby reducing the COF. The shear behavior of adsorbed ions in electrolyte solution is sensitive to their valence, because of their different surface force contribution. The study further provides a framework to optimize the design of hydration lubrication.

Lubricating Microneedles System with Multistage Sustained Drug Delivery for the Treatment of Osteoarthritis.

Osteoarthritis (OA) is a typical joint degenerative disease that is prevalent worldwide and significantly affects the normal activities of patients. Traditional treatments using diclofenac (DCF) as an anti-inflammatory drug by oral administration and transdermal delivery have many inherent deficiencies. In this study, a lubricating microneedles (MNs) system for the treatment of osteoarthritis with multistage sustained drug delivery and great reduction in skin damage during MNs penetration is developed. The bilayer dissolvable MNs system, namely HA-DCF@PDMPC, is prepared by designating the composite material of hyaluronic acid (HA) and covalently conjugated drug compound (HA-DCF) as the MNs tips and then modifying the surface of MNs tips with a self-adhesive lubricating copolymer (PDMPC). The MNs system is designed to achieve sustained drug release of DCF via ester bond hydrolysis, physical diffusion from MNs tips, and breakthrough of lubrication coating. Additionally, skin damage is reduced due to the presence of the lubrication coating on the superficial surface. Therefore, the lubricating MNs with multistage sustained drug delivery show good compliance as a transdermal patch for OA treatment, which is validated from anti-inflammatory cell tests and therapeutic animal experiments, down-regulating the expression levels of pro-inflammatory factors and alleviating articular cartilage destruction.

An "All-in-One" Strategy to Reconstruct Temporomandibular Joint Osteoarthritic Microenvironment Using γ-Fe2O3@TA@ALN Nanoparticles.

Current clinical strategies for the treatment of temporomandibular joint osteoarthritis (TMJOA) primarily target cartilage biology, overlooking the synergetic effect of various cells and inorganic components in shaping the arthritic microenvironment, thereby impeding the effectiveness of existing therapeutic options for TMJOA. Here, γ-Fe2O3@TA@ALN magnetic nanoparticles (γ-Fe2O3@TA@ALN MNPs) composed of γ-Fe2O3, tannic acid (TA), and alendronate sodium (ALN) are engineered to reconstruct the osteoarthritic microenvironment and mitigate TMJOA progression. γ-Fe2O3@TA@ALN MNPs can promote chondrocytes' proliferation, facilitate chondrogenesis and anisotropic organization, enhance lubrication and reduce cartilage wear, and encourage cell movement. Magnetic-responsive γ-Fe2O3@TA@ALN MNPs also exhibit pH sensitivity, which undergoes decomposition within acidic environment to release ALN on demand. Under a 0.2 T static magnetic field, γ-Fe2O3@TA@ALN MNPs accelerate the synthesis of cartilage-specific proteins, and suppress catabolic-related genes expression and reactive oxygen species generation, affording additional protection to TMJ cartilage. In TMJOA mouse models, articular injection of γ-Fe2O3@TA@ALN MNPs effectively alleviates cartilage degeneration and subchondral bone loss in short and long terms, offering promising avenues for the development of therapeutic interventions for TMJOA.

Toward Defect-Free Nanoimprinting.

Nanoimprinting large-area structures, especially high-density features like meta lenses, poses challenges in achieving defect-free nanopatterns. Conventional high-resolution molds for nanoimprinting are often expensive, typically constructed from inorganic materials such as silicon, nickel (Ni), or quartz. Unfortunately, replicated nanostructures frequently suffer from breakage or a lack of definition during demolding due to the high adhesion and friction at the polymer-mold interface. Moreover, mold degradation after a limited number of imprinting cycles, attributed to contamination and damaged features, is a common issue. In this study, a disruptive approach is presented to address these challenges by successfully developing an anti-sticking nanocomposite mold. This nanocomposite mold is created through the co-deposition of nickel atoms and low surface tension polytetrafluoroethylene (PTFE) nanoparticles via electroforming. The incorporation of PTFE enhances the ease of polymer release from the mold. The resulting Ni-PTFE nanocomposite mold exhibits exceptional lubrication properties and a significantly reduced surface energy. This robust nanocomposite mold proves effective in imprinting fine, densely packed nanostructures down to 100 nm using thermal nanoimprinting for at least 20 cycles. Additionally, UV nanoimprint lithography (UV-NIL) is successfully performed with this nanocomposite mold. This work introduces a novel and cost-effective approach to reusable high-resolution molds, ensuring defect-reduction production in nanoimprinting.

Robust and Lubricating Interface Semi-Interpenetrating Network on Inert Polymer Substrates Enabled by Subsurface-Initiated Polymerization.

Lubricating hydrogel coatings on inert rubber and plastic surfaces significantly reduce friction and wear, thus enhancing material durability and lifespan. However, achieving optimal hydration lubrication typically requires a porous polymer network, which unfortunately reduces their mechanical strength and limits their applicability where robust durability and wear-resistance are essential. In the research, a hydrogel coating with remarkable wear resistance and surface stability is developed by forming a semi-interpenetrating polymer network with polymer substrate at the interface. By employing a good solvent swelling method, monomers, and photoinitiators are embedded within the substrates' subsurface, followed by in situ polymerization under ultraviolet light, creating a robust semi-interpenetrating and entangled network structure. This approach, offering a thicker energy-dissipating layer, outperforms traditional surface modifications in wear resistance while preserving anti-fatigue, hydrophilicity, oleophobicity, and other properties. Adaptable to various rubber and plastic substrates by using suitable solvents, this method provides an efficient solution for creating durable, lubricating surfaces, broadening the potential applications in multiple industries.

Electrostatically Self-Assembled Magnetic Nanoparticles for High-Temperature Resistant and Friction-Controlled Lubrication System.

Magnetic-responsive surfactants are considered promising smart lubricating materials due to their significant stimulation response to applied magnetic fields. In this study, four magneto-responsive surfactants are successfully fabricated and encapsulated on the surface of molybdenum disulfide nanosheets (MoS2@C18H37N+(CH3)3[XCl3Br]-, X = Fe, Ce, Gd, and Ho) as base-oil components using electrostatic self-assembly, thereby constructing a multi-functional magnetic lubrication system (MoS2@STAX). Magnetorheological measurements confirm the remarkable responsiveness of MoS2@STACe lubricants at high shear rates and applied magnetic fields, which is further corroborated by the constant proximity of the magnet. The formation of dense carbon and tribo-chemical films between the friction interfaces at elevated temperatures is the primary factor contributing to the significant reduction in frictional wear. Notably, the magnetic lubricant demonstrates a pronounced response behavior when subjected to an applied magnetic field in the ceramic tribopair, even at lower magnetic fields. This work presents concepts for the development of high-temperature resistant and tunable lubrication additives by designing the material structure and controlling the magnetic stimulation.

Modulating mechanobiology as a therapeutic target for synovial fibrosis to restore joint lubrication.

OBJECTIVES: Fibroses are disorders linked to persistence of myofibroblasts due to biochemical (e.g., Transforming growth factor-ß) and biophysical cues (e.g., a stiff microenvironment). In the context of osteoarthritis, fibrotic changes in the joint-lining synovium have been linked with disease progression. The objective of this study was to probe synovial fibroblast mechanobiology and how essential functions (i.e., lubrication) are altered in fibrotic environments. DESIGN: Both ex vivo and in vitro synovium models were assessed for fibrotic and lubrication biomarkers to better understand the role of mechanobiology and lubrication. Additionally, in vitro, work on small molecules targeting mechanobiology was assessed. RESULTS: Our results indicated that modulating mechanobiology could rescue the fibrotic phenotype instigated by stiffening microenvironment that resulted in altered lubricant expression. A small molecule therapeutic, fasudil, blocked ROCK-mediated contractility and this inhibition of the fibrotic mechano-response of synovial fibroblasts restored proper lubrication function, providing insight into mechanisms of disease progression as well as a new avenue for therapeutic development. CONCLUSION: This study identifies synovial fibrosis as a condition that potentially has joint-wide deficits through inhibiting lubrication. Additionally, modulating mechanobiology (i.e., ROCK-mediated contractility) may pose a potential target for small molecule therapies that can be delivered to the joint space. CLASSIFICATION: Applied Biological Sciences.

Astringency and its sub-qualities: a review of astringency mechanisms and methods for measuring saliva lubrication.

Astringency is an important mouthfeel attribute that influences the sensory experiences of many food and beverage products. While salivary lubricity loss and increased oral friction were previously believed to be the only astringency mechanisms, recent research has demonstrated that nontactile oral receptors can trigger astringency by responding to astringents without mechanical stimulation. Various human factors have also been identified that affect individual responses to astringents. This article presents a critical review of the key research milestones contributing to the current understanding of astringency mechanisms and the instrumental approaches used to quantify perceived astringency intensity. Although various chemical assays or physical measures mimic in-mouth processes involved in astringent mouthfeel, this review highlights how one chemical or physical approach can only provide a single measure of astringency determined by a specific mechanism. Subsequently, using a single measurement to predict astringency perception is overly idealistic. Astringency has not been quantified beyond the loss of saliva lubrication; therefore, nontactile receptor-based responses must also be explored. An important question remains about whether astringency is a single perception or involves distinct sub-qualities such as pucker, drying, and roughness. Although these sub-quality lexicons have been frequently cited, most studies currently view astringency as a single perception rather than dividing it into sub-qualities and investigating the potentially independent mechanisms of each. Addressing these knowledge gaps should be an important priority for future research.

Simulation-based research on enhancing lubricity: investigating wettability and textured surfaces in alkane lubricants under boundary lubrication conditions.

Changing the wettability and surface texturing have a significant impact on lubrication. In this study, the researchers used the molecular dynamics method to investigate how adjusting the interaction between alkanes and the wall affects oil film morphology and frictional properties under boundary lubrication. The findings revealed that the bearing capacity was influenced by both the morphology of the oil film and the strength of solid-liquid adsorption. In cases where the walls had weak wettability, the alkanes formed clusters to effectively separate the walls, while in cases where the walls had strong wettability, the oil film spread and formed a strong adsorption film. The super oleophilic textured surface could enhance the oil film adsorption capacity and replenish the oil film to the friction area in time, and the super oleophobic smooth surface could further reduce the friction coefficient. Therefore, a composite surface consisting of a super oleophilic textured surface and a super oleophobic smooth surface can be designed to enhance the bearing capacity of the oil film and reduce friction.

Design and tribological performance of graphene nanofluids dispersed by dragging effect of bicomponent gelator.

Nanofluids have excellent lubrication and high thermal conductivity. However, the agglomeration and sedimentation produced by the large surface energy of nanoparticles in base liquid threaten the long-term dispersion stability and impact the wide application of nanofluid. In this work, based on the self-assemble behavior and continuous network structure formed by low molecular weight organic gelator, the uniform clusters were formed through regulating the kinetics behavior in the gelling process. The dragging effect was demonstrated by oleic acid - sodium dodecyl sulfate (OA-SDS) bicomponent gelator and graphene oxide (GO) nanosheets. The results showed that GO nanofluids dispersed by OA-SDS were stable for more than 12 months. The well-dispersed GO nanofluid exhibited better anti-friction and anti-wear properties under both immersion and electrostatic minimum quantity lubrication conditions. Moreover, the lower contact angle, surface tension and droplet size of nanofluids after charging improved the wettability on the frictional interface. The GO adsorption film formed on the friction interface protected the tribochemical reaction film of iron oxide and prevented the occurrence of sintering of base oil.

Biocompatible Solutions: Evaluating the Safety of Repeated Intra-Articular Injections of pMPCylated Liposomes for Knee Osteoarthritis Therapy in Rat Models.

Knee osteoarthritis (OA) poses a significant health care burden globally, necessitating innovative therapeutic approaches. CCoat, a novel poly(2-[methacryloyloxy]ethyl phosphorylcholine) (pMPC)ylated liposome device, protects the cartilage surface of the joint from mechanical wear through an entropy-favored process. Two preclinical studies were performed to explore the safety of CCoat following repeated intra-articular (IA) injections into the knee joint (i.e., femorotibial joint) in Sprague-Dawley rats. The studies involved 2 or 3 IA injections, at an interval of 2 or 3 weeks, and an observation period of 1 or 13 weeks after the last injection. Assessments included clinical, histopathological, and immunofluorescent evaluations. In study 1, no mortality or abnormal clinical signs occurred. At 1 week post last injection, histopathology revealed minimal vacuolated macrophages beneath the synovial membrane, predominantly M2-like, indicating a nonadverse response. Immunofluorescent staining supported M2-like macrophage predominance. Study 2 confirmed these findings with no systemic effects over 13 weeks. Statistical analyses indicated no significant differences in body weight, clinical pathology, or organ weights compared with controls. Results affirming the safety of pMPCylated liposomes following repeated IA injections in rat. This novel lubricant coating approach shows promise in OA therapy, with this safety assessment supporting its potential clinical application.

Construction of Zwitterionic Coatings with Lubricating and Antiadhesive Properties for Invisible Aligner Applications.

Invisible aligners have been widely used in orthodontic treatment but still present issues with plaque formation and oral mucosa abrasion, which can lead to complicated oral diseases. To address these issues, hydrophilic poly(sulfobetaine methacrylate) (polySBMA) coatings with lubricating, antifouling, and antiadhesive properties have been developed on the aligner materials (i.e., polyethylene terephthalate glycol, PETG) via a simple and feasible glycidyl methacrylate (GMA)-assisted coating strategy. Poly(GMA-co-SBMA) is grafted onto the aminated PETG surface via the ring-opening reaction of GMA (i.e., "grafting to" approach to obtain G-co-S coating), or a polySBMA layer is formed on the GMA-grafted PETG surface via free radical polymerization (i.e., "grafting from" approach to obtain G-g-S coating). The G-co-S and G-g-S coatings significantly reduce the friction coefficient of PETG surface. Protein adsorption, bacterial adhesion, and biofilm formation on the G-co-S- and G-g-S-coated surfaces are significantly inhibited. The performance of the coatings remains stable after storage in air or artificial saliva for 2 weeks. Both coatings demonstrate good biocompatibility in vitro and is not caused irritation to the oral mucosa of rats in vivo over 2 weeks. This study proposes a promising strategy for the development of invisible aligners with improved performance, which is beneficial for oral health treatment.

Surface-Templated Polymer Microparticle Synthesis Based on Droplet Microarrays.

Polymer microparticle synthesis based on the surface-templated method is a simple and environmentally friendly method to produce various microparticles. Unique particles with different compositions can be fabricated by simply annealing a polymer on a liquid-repellent surface. However, there are hurdles to producing particles of homogeneous sizes with large quantities and varying the shape of particles. Here, a new approach to synthesizing multiple polymer microparticles using micropatterns with wettability contrast is presented. Polymer microparticles are formed in two steps. First, a layer of poly(sodium-4-styrenesulfonate) is deposited on the hydrophilic regions by dipping and withdrawing this micropattern from a polymer solution, and an array of microdroplets is formed. A dewetting-inducing layer on the pattern is introduced, and then target polymer patches are sequentially generated on it. By annealing over Tg, the contact line of the target polymer patch is freely receded, creating a particle form. The size and shape of the microparticle can be controlled by varying the micropatterns. In addition, it is demonstrated that microparticles made of polymer blends or polymer/nanoparticle composite are easily produced. This versatile method offers the potential of surface-templated synthesis to tailor polymer microparticles with different sizes, shapes, and functionalities in various research and applications.

Modelling Mucus Clearance in Sinuses: Thin-Film Flow Inside a Fluid-Producing Cavity Lined with an Active Surface.

The paranasal sinuses are a group of hollow spaces within the human skull, surrounding the nose. They are lined with an epithelium that contains mucus-producing cells and tiny hairlike active appendages called cilia. The cilia beat constantly to sweep mucus out of the sinus into the nasal cavity, thus maintaining a clean mucus layer within the sinuses. This process, called mucociliary clearance, is essential for a healthy nasal environment and disruption in mucus clearance leads to diseases such as chronic rhinosinusitis, specifically in the maxillary sinuses, which are the largest of the paranasal sinuses. We present here a continuum mathematical model of mucociliary clearance inside the human maxillary sinus. Using a combination of analysis and computations, we study the flow of a thin fluid film inside a fluid-producing cavity lined with an active surface: fluid is continuously produced by a wall-normal flux in the cavity and then is swept out, against gravity, due to an effective tangential flow induced by the cilia. We show that a steady layer of mucus develops over the cavity surface only when the rate of ciliary clearance exceeds a threshold, which itself depends on the rate of mucus production. We then use a scaling analysis, which highlights the competition between gravitational retention and cilia-driven drainage of mucus, to rationalise our computational results. We discuss the biological relevance of our findings, noting that measurements of mucus production and clearance rates in healthy sinuses fall within our predicted regime of steady-state mucus layer development.

Exogenous Collagen Crosslinking is Highly Detrimental to Articular Cartilage Lubrication.

Healthy articular cartilage is a remarkable bearing material optimized for near-frictionless joint articulation. Because its limited self-repair capacity renders it susceptible to osteoarthritis (OA), approaches to reinforce or rebuild degenerative cartilage are of significant interest. While exogenous collagen crosslinking (CXL) treatments improve cartilage's mechanical properties and increase its resistance to enzymatic degradation, their effects on cartilage lubrication remain less clear. Here, we examined how the collagen crosslinking agents genipin (GP) and glutaraldehyde (GTA) impact cartilage lubrication using the convergent stationary contact area (cSCA) configuration. Unlike classical configurations, the cSCA sustains biofidelic kinetic friction coefficients (µk) via superposition of interstitial and hydrodynamic pressurization (i.e., tribological rehydration). As expected, glutaraldehyde- and genipin-mediated CXL increased cartilage's tensile and compressive moduli. Although net tribological rehydration was retained after CXL, GP or GTA treatment drastically elevated µk. Both healthy and "OA-like" cartilage (generated via enzymatic digestion) sustained remarkably low µk in saline- (≤0.02) and synovial fluid-lubricated contacts (≤0.006). After CXL, µk increased up to 30-fold, reaching values associated with marked chondrocyte death in vitro. These results demonstrate that mechanical properties (i.e., stiffness) are necessary, but not sufficient, metrics of cartilage function. Furthermore, the marked impairment in lubrication suggests that CXL-mediated stiffening is ill-suited to cartilage preservation or joint resurfacing.

Electrochemical Investigation of the Stability of Poly-Phosphocholinated Liposomes.

Poly[2-(methacryloyloxy)ethyl phosphorylcholine] liposomes (pMPC liposomes) gained attention during the last few years because of their potential use in treating osteoarthritis. pMPC liposomes that serve as boundary lubricants are intended to restore the natural lubrication properties of articular cartilage. For this purpose, it is important that the liposomes remain intact and do not fuse and spread as a lipid film on the cartilage surface. Here, we investigate the stability of the liposomes and their interaction with two types of solid surfaces, gold and carbon, by using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). With the aid of a hydrophilic species used as an electroactive probe in the solution, the charge transfer characteristics of the electrode surfaces are obtained. Additionally, from EIS, the capacitance characteristics of the surfaces are derived. No decrease of the peak currents and no displacement of the peak potentials to greater overpotentials are observed in the CV experiments. No decrease in the apparent capacitance and increase in the charge transfer resistance is observed in the EIS experiments. On the contrary, all parameters in both CV and EIS do change in the opposite direction. The obtained results confirm that there is only physical adsorption without fusion and spreading of the pMPC liposomes and without the formation of lipid films on the surfaces of both gold and carbon electrodes.

Highly Interfacial Active Gemini Surfactants as Simple and Versatile Emulsifiers for Stabilizing, Lubricating and Structuring Liquids.

To date, locking the shape of liquids into non-equilibrium states usually relies on jamming nanoparticle surfactants at an oil/water interface. Here we show that a synthetic water-soluble zwitterionic Gemini surfactant can serve as an alternative to nanoparticle surfactants for stabilizing, structuring and additionally lubricating liquids. By having a high binding energy comparable to amphiphilic nanoparticles at the paraffin oil/water interface, the surfactant can attain near-zero interfacial tensions and ultrahigh surface coverages after spontaneous adsorption. Owing to the strong association between neighboring surfactant molecules, closely packed monolayers with high mechanical elasticity can be generated at the oil/water interface, thus allowing the surfactant to produce not only ultra-stable emulsions but also structured liquids with various geometries by using extrusion printing and 3D printing techniques. By undergoing tribochemical reactions at its sulfonic terminus, the surfactant can endow the resultant emulsions with favorable lubricity even under high load-bearing conditions. Our study may provide new insights into creating complex liquid devices and new-generation lubricants capable of combining the characteristics of both liquid and solid lubricants.