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.

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.

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.

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.

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.

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.

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.

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.

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.

Role of segmental contraction in the small intestinal digestion: A computational approach to study the physics behind the luminal mixing and transport.

Segmentation is well known to digest the food rich in proteins, starch, and lipids; however, the mechanism leading to the digestion remains unclear. In this study, a theoretical model for segmental contractions of the small intestine is developed using lubrication method to explore the mechanisms involved. Here, the nonlinear partial differential equations governing the fluid flow were normalized in viscous regime and solved semi-analytically for a power law fluid under long wavelength approximation on a MatlabTM platform. Study indicates that shearing is highest at the 1st and 4th mid-occlusion in comparison to 2nd and 3rd mid-occlusion. Parametric study indicates that the flow is sensitive to - the span of segmentation or wavelength of the wave, occlusion of the wave and frequency of the contraction; with shearing being highest for dilatants. Shearing is more prominent at higher occlusion (>50 %) and frequency (>6Hz). Further, mixing is more prominent at the steep regions of the wave; having intensity of mixing highest for the outer waves in comparison to waves at mid-region of the segmentation. The power demand is found to be greater in segmentation and has the following precedence - frequency, wavelength, flow behavior index, and occlusion (up to 80 %). Further, multiplicity of the wave gives rise to multiple zones of mixing which increases the rate of mixing of the contents. Suggesting that, the segmentation primarily serves the purpose of mixing. The study will be useful to explore novel therapeutic strategies of managing patients suffering from various motility-associated disorders of the small intestine.

Methamphetamine-induced vaginal lubrication in rats.

BACKGROUND: Based on previous studies of vaginal lubrication as well as our own previously reported interview study of women who self-reported methamphetamine (meth)-induced vaginal lubrication, in the current study we sought to determine the potential dose-response relationship leading to meth-induced vaginal lubrication. We also developed an animal model to study the reported effects and examine potential mechanisms mediating this phenomenon. AIM: We sought to characterize the effects of meth on vaginal lubrication in an animal model with the aim of providing a potential framework for new mechanisms that incorporate novel therapeutic agents for the treatment of vaginal dryness. METHODS: Vaginal lubrication was measured via insertion of a preweighed, cotton-tipped swab into the vaginal canal of anesthetized rats following treatment with various doses of intravenous (IV) meth, up to 0.96 mg/kg, and after additional pharmacological manipulations, including administration of a nitric oxide synthase inhibitor and an estrogen receptor antagonist. Plasma signaling molecules, including estradiol, progesterone, testosterone, nitric oxide, and vasoactive intestinal polypeptide, were measured immediately before and at 9 time points after IV meth administration. Blood was collected via a previously implanted chronic indwelling jugular catheter and analyzed by use of commercially available kits per the manufacturer's instructions. OUTCOMES: Outcomes for this study include the measurement of vaginal lubrication in anesthetized rats following various pharmacological manipulations and plasma levels of various signaling molecules. RESULTS: Meth dose-dependently increased vaginal lubrication in anesthetized female rats. Meth significantly increased plasma levels compared to baseline of estradiol (2 and 15 minutes after meth infusion) as well as progesterone, testosterone, and nitric oxide (10 minutes after meth infusion). Also, vasoactive intestinal polypeptide decreased significantly compared to baseline for 45 minutes following meth infusion. Our data further suggest that nitric oxide, but not estradiol, is critical in the production of vaginal secretions in response to meth. CLINICAL IMPLICATIONS: This study has far-reaching implications for women who are suffering from vaginal dryness and for whom estrogen therapy is unsuccessful, as the investigation has demonstrated that meth presents a novel mechanism for producing vaginal lubrication that can be targeted pharmacologically. STRENGTHS AND LIMITATIONS: This study is, to our knowledge, the first performed to measure the physiological sexual effects of meth in an animal model. Animals were anesthetized when they were administered meth. In an ideal situation, animals would be self-administering the drug to recapitulate better the contingent nature of drug taking; however, this method was not feasible for the study reported here. CONCLUSION: Methamphetamine increases vaginal lubrication in female rats through a nitric oxide-dependent mechanism.

Fibromyalgia syndrome is associated with sexual dysfunction regardless of physical activity status: a cross-sectional study.

BACKGROUND: Fibromyalgia syndrome (FMS) is a rheumatic disorder that has been observed to affect self-perception of sexuality. AIM: The study aims to assess sexual dysfunction (SD), establish possible associations with SD levels, and evaluate the impact of physical activity (PA) levels on SD in Spanish women with FMS as compared with healthy control women. METHODS: The study was cross-sectional. A total of 170 women voluntarily agreed to participate between September 2019 and February 2020: 88 in the FMS group and 82 in the control group. OUTCOMES: The main outcome measures were SD, as assessed through the Female Sexual Function Index (FSFI), and PA levels, as assessed with a structured interview. RESULTS: There were significant differences in every domain and total SD score between the FMS and control groups (P < .05). In addition, we obtained a moderate significant direct association (χ2[1] = 37.071, P < .05, phi = 0.467) when exploring the associations between FMS and risk of SD. Results showed statistically significant differences between the FMS group and the control group when PA levels were not reached in the desire, pain, and total scores of the FSFI (P < .05). When the PA levels were reached, between-group differences were found in all domains, as well as in the total score of the FSFI (P < .05). CLINICAL IMPLICATIONS: Sexual function should be evaluated in women with FMS, while future treatments should address this clinical area with the aim of managing SD in this population. STRENGTHS AND LIMITATIONS: The main limitation is that the outcome measures were self-reported. CONCLUSION: We found a high prevalence of SD in Spanish women with FMS, with an impact on aspects such as desire, arousal, lubrication, orgasm, satisfaction, and pain during sexual intercourse. In addition, there is a moderate direct association between FMS and SD. Ultimately, the results showed that, irrespective of PA, women with FMS reported increased SD.

Investigation of Dispersion Kinetics of Particulate Lubricants and their Effect on the Mechanical Strength of MCC Tablets.

INTRODUCTION: Tablets are commonly produced by internally adding particulate lubricants, which are known to possibly lower the mechanical strength of tablets. This reduction is caused by the coverage of matrix forming components by lubricant particles, resulting in decreased interparticulate interactions. The known incompatibilities with some active compounds of the predominantly used lubricant, magnesium stearate, call for the in-depth characterization of alternative lubricants. PURPOSE: Investigation of the dispersion behavior of five commonly applied pharmaceutical lubricants by mathematically modeling the dispersion kinetics for short and extended mixing times. METHODS: The dispersion behavior of five different pharmaceutical lubricants were examined by systematically varying lubricant concentration and mixing time of binary formulations and evaluating the kinetic of tensile strength reduction by theoretically estimating the surface coverage based on particle sizes. RESULTS: For short mixing times, a unifying relationship between compactibility reduction and theoretical surface coverage was identified. Subsequently, for extended mixing times, distinct differences in the shear strength and dispersion kinetics of the investigated lubricants were found. CONCLUSIONS: The lubricant particle size controls the tensile strength reduction if short mixing times are applied. For extended mixing times, the investigated lubricants can be divided into two groups in terms of dispersion kinetics. Possible underlying reasons are discussed in detail in order to enhance the general understanding of lubricant dispersions in tablet formulations.

Decoding the phonon transport of structural lubrication at silicon/silicon interface.

Although the friction characteristics under different contact conditions have been extensively studied, the mechanism of phonon transport at the structural lubrication interface is not extremely clear. In this paper, we firstly promulgate that there is a 90°-symmetry of friction force depending on rotation angle at Si/Si interface, which is independent of normal load and temperature. It is further found that the interfacial temperature difference under incommensurate contacts is much larger than that in commensurate cases, which can be attributed to the larger interfacial thermal resistance (ITR). The lower ITR brings greater energy dissipation in commensurate sliding, and the reason for that is more effective energy dissipation channels between the friction surfaces, making it easier for the excited phonons at the washboard frequency and its harmonics to transfer through the interface. Nevertheless, the vibrational frequencies of the interfacial atoms between the tip and substrate during the friction process do not match in incommensurate cases, and there is no effective energy transfer channel, thus presenting the higher ITR and lower friction. Eventually, the number of excited phonons on contact surfaces reveals the amount of frictional energy dissipation in different contact states.

Polyelectrolyte-Functionalized NanoMOFs for Highly Efficient Aqueous Lubrication and Sustained Drug Release.

This study demonstrates the hybridization of polyelectrolyte brushes with anti-inflammatory drug-loaded nanoMOFs that can achieve highly efficient aqueous lubrication and sustained drug release for the synergistic therapy of osteoarthritis (OA). Poly(3-sulfopropyl methacrylate potassium salt) (PSPMK) brushes are grown on the surface of the UiO-66-NH2 via one-pot grafting polymerization, which served as a general surface modification method of NH2 -MOFs to grow the polymer brushes. The growth of the PSPMK brushes greatly enhance the stability, dispersity, and swollen property of the AS-UiO-66-NH2@PSPMK in aqueous media. Using as lubricating additives, the UiO-66-NH2 @PSPMK achieves not only reductions in both coefficient of friction and wear volume over 70% and 99% but also supports high load-carrying capacity and long-term durability. The PSPMK brushes can be served as an universal interfacial modification soft layer that can significantly improve the aqueous lubricating performance of other types of NH2 -MOFs. After encapsulating the anti-inflammatory aspirin (AS), the AS-UiO-66-NH2 @PSPMK shows both sustained drug release and good biocompatibility toward the human normal chondrocytes. This work establishes anti-inflammatory drug-loaded UiO-66-NH2 @PSPMK as a potential multifunctional joint lubricant for OA treatment.

On the role of cell surface associated, mucin-like glycoproteins in the pennate diatom Craspedostauros australis (Bacillariophyceae).

Diatoms are single-celled microalgae with silica-based cell walls (frustules) that are abundantly present in aquatic habitats, and form the basis of the food chain in many ecosystems. Many benthic diatoms have the remarkable ability to glide on all natural or man-made underwater surfaces using a carbohydrate- and protein-based adhesive to generate traction. Previously, three glycoproteins, termed FACs (Frustule Associated Components), have been identified from the common fouling diatom Craspedostauros australis and were implicated in surface adhesion through inhibition studies with a glycan-specific antibody. The polypeptide sequences of FACs remained unknown, and it was unresolved whether the FAC glycoproteins are indeed involved in adhesion, or whether this is achieved by different components sharing the same glycan epitope with FACs. Here we have determined the polypeptide sequences of FACs using peptide mapping by LC-MS/MS. Unexpectedly, FACs share the same polypeptide backbone (termed CaFAP1), which has a domain structure of alternating Cys-rich and Pro-Thr/Ser-rich regions reminiscent of the gel-forming mucins. By developing a genetic transformation system for C. australis, we were able to directly investigate the function of CaFAP1-based glycoproteins in vivo. GFP-tagging of CaFAP1 revealed that it constitutes a coat around all parts of the frustule and is not an integral component of the adhesive. CaFAP1-GFP producing transformants exhibited the same properties as wild type cells regarding surface adhesion and motility speed. Our results demonstrate that FAC glycoproteins are not involved in adhesion and motility, but might rather act as a lubricant to prevent fouling of the diatom surface.

Pore-size dependence and slow relaxation of hydrogel friction on smooth surfaces.

Hydrogels consist of a cross-linked polymer matrix imbibed with a solvent such as water at volume fractions that can exceed 90%. They are important in many scientific and engineering applications due to their tunable physiochemical properties, biocompatibility, and ultralow friction. Their multiphase structure leads to a complex interfacial rheology, yet a detailed, microscopic understanding of hydrogel friction is still emerging. Using a custom-built tribometer, here we identify three distinct regimes of frictional behavior for polyacrylic acid (PAA), polyacrylamide (PAAm), and agarose hydrogel spheres on smooth surfaces. We find that at low velocities, friction is controlled by hydrodynamic flow through the porous hydrogel network and is inversely proportional to the characteristic pore size. At high velocities, a mesoscopic, lubricating liquid film forms between the gel and surface that obeys elastohydrodynamic theory. Between these regimes, the frictional force decreases by an order of magnitude and displays slow relaxation over several minutes. Our results can be interpreted as an interfacial shear thinning of the polymers with an increasing relaxation time due to the confinement of entanglements. This transition can be tuned by varying the solvent salt concentration, solvent viscosity, and sliding geometry at the interface.