Adsorption and friction behavior of amphiphilic polymers on hydrophobic surfaces.

The ability of amphiphilic polymers to self-assemble and form a gel or gel-like layer has been investigated by means of both experimental and theoretical studies on alkylated derivatives of poly(acrylic acid). Experiments were performed to determine the relationship between amphiphilic polymer chemistry, structure, water retention, and friction in the presence of hydrophobic substrates. The results indicate that the amphiphilic polymer forms a water-enriched, friction-reducing adsorbed layer on hydrophobic surfaces. The shear moduli and viscosities of the adsorbed layers, as determined by fitting the Voigt model to QCM-D data, were consistent with the presence of a gel. Computational studies on HPAA-12 were performed and are consistent with the presence of adsorbed conformations, in which the lowest free energy in the model corresponded to a partially adsorbed molecule, with a small fraction of hydrophobic side chains being compelled, for configurational reasons, to point into the bulk water. This would support the possibility of the formation of either a gel-like layer or surface aggregation. However, because the adsorption experiments showed no evidence of aggregation, this strongly suggests the formation of a gel.

Liposomal aggregates sustain the release of rapamycin and protect cartilage from friction.

Liposomes show promise as biolubricants for damaged cartilage, but their small size results in low joint and cartilage retention. We developed a zinc ion-based liposomal drug delivery system for local osteoarthritis therapy, focusing on sustained release and tribological protection from phospholipid lubrication properties. Our strategy involved inducing aggregation of negatively charged liposomes with zinc ions to extend rapamycin (RAPA) release and improve cartilage lubrication. Liposomal aggregation occurred within 10 min and was irreversible, facilitating excess cation removal. The aggregates extended RAPA release beyond free liposomes and displayed irregular morphology influenced by RAPA. At nearly 100 µm, the aggregates were large enough to exceed the previously reported size threshold for increased joint retention. Tribological assessment on silicon surfaces and ex vivo porcine cartilage revealed the system's excellent protective ability against friction at both nano- and macro-scales. Moreover, RAPA was shown to attenuate the fibrotic response in human OA synovial fibroblasts. Our findings suggest the zinc ion-based liposomal drug delivery system has potential to enhance OA therapy through extended release and cartilage tribological protection, while also illustrating the impact of a hydrophobic drug like RAPA on liposome aggregation and morphology.

Conformal Bacterial Cellulose Coatings as Lubricious Surfaces.

We report a versatile method to form bacterial cellulose coatings through simple dip-coating of 3D objects in suspensions of cellulose-producing bacteria. The adhesion of cellulose-secreting bacteria on objects was promoted through surface roughness and chemistry. Immobilized bacteria secreted highly porous hydrogels with high water content directly from the surface of a variety of materials. The out-of-plane orientation of cellulose fibers present in this coating leads to high mechanical stability and energy dissipation with minimal cellulose concentration. The conformal, biocompatible, and lubricious nature of the in situ grown cellulose surfaces makes the coated 3D objects attractive for biomedical applications.

The adsorption and lubrication behavior of synovial fluid proteins and glycoproteins on the bearing-surface materials of hip replacements.

The selectivity of synovial fluid protein adsorption onto ultra-high molecular weight polyethylene (UHMWPE) and alumina (Al(2)O(3)), and in particular the ability of glycoproteins to adsorb in the presence of all the other synovial fluid proteins, was investigated by means of fluorescence microscopy and gel electrophoresis (SDS-PAGE). The non-specific nature of protein adsorption from synovial fluid indicated that the lubrication of artificial hip-joint materials may not be attributable to a single protein as has been frequently suggested. The friction behavior of polyethylene (PE) sliding against Al(2)O(3) in solutions of bovine serum albumin (BSA), alpha-1-acid glycoprotein (AGP) and alpha-1-antitrypsin (A1AT) was investigated by means of colloidal probe atomic force microscopy. BSA was shown to be a poorer boundary lubricant than the phosphate buffered saline used as a control. This was attributed to denaturation of the BSA upon adsorption, which provided a high-shear-strength layer at the interface, impairing the lubrication. Interestingly, both the glycoproteins AGP and A1AT, despite their low concentrations, improved lubrication. The lubricating properties of AGP and A1AT were attributed to adsorption via the hydrophobic backbone, allowing the hydrophilic carbohydrate moieties to be exposed to the aqueous solution, thus providing a low-shear-strength fluid film that lubricated the system. The amount of glycoprotein adsorbed on hydrophobic surfaces was determined by means of optical waveguide lightmode spectroscopy (OWLS), allowing conclusions to be drawn about the conformation of the glycan residues following adsorption.

Friction, lubrication, and polymer transfer between UHMWPE and CoCrMo hip-implant materials: a fluorescence microscopy study.

The friction coefficients of CoCrMo sliding against UHMWPE and CoCrMo were measured in solutions of albumin and synovial fluid containing fluorescently labeled albumin. No fluorescence could be observed on the CoCrMo disc following incubation in labeled albumin or after sliding against CoCrMo. This was due to quenching of the fluorophore by the metal and indicated that a protein film thicker than 10 nm was not formed on the surface. A more complicated behavior was observed for UHMWPE sliding against CoCrMo. For each lubricating solution and at each load, a bimodal distribution of steady-state friction values was observed, the friction coefficient either remaining constant or decreasing during the early stages of the measurement. As no quenching of the fluorophores occurred on the UHMWPE surface, the fluorescence labeling method could be used to reveal polyethylene (PE) transfer and to show that it correlates with the friction coefficient: Low friction coefficients corresponded to a low density of PE spots on the CoCrMo surface. In addition, it was found that the friction coefficients for UHMWPE sliding against CoCrMo in synovial fluid were not significantly different from those in phosphate-buffered saline (PBS), but that the addition of albumin to PBS did cause a significant increase in the friction coefficient.