Mechanics and tribology of a zwitterionic polymer blend: Impact of molecular weight.

Despite decades of biomimetic materials development, the tribological properties of articular cartilage remain unrivalled. This manuscript presents the design and material properties of a polymer blend composed of poly (vinyl alcohol) (PVA) and a zwitterionic polysulfobetaine (PMEDSAH) prepared into hydrogel form using a cyclic freeze-thaw method. The PVA hydrogel matrix provides mechanical strength while the zwitterionic polymer, PMEDSAH, is intended to act as a boundary lubricant. The formation of PVA-PMEDAH hydrogel blends was found to result in unique biomimetic system where the boundary lubricant elutes from the bulk material to the surface in response to applied pressure. This behavior is attributed to the high-water content of the PVA hydrogel matrix and the solubility of PMEDSAH in aqueous solution. In addition to characterizing the effects of boundary lubricant molecular weight on the diffusive properties of the hydrogel blend, we report the coefficient of friction, µ, versus sliding speed for the hydrogel/glass interface. Consistent with our prior findings, PMEDSAH was found to engender lubricious behavior and the dependence of µ on sliding velocity indicated a repulsive interaction with glass rather than an attractive one. This result agrees with the hydration lubrication hypothesis. Contact mechanics analyzed within the context of Hertzian biphasic theory were also investigated, revealing that the introduction of PMEDSAH enhances the hydrogel's ability to provide interstitial fluid load support.

Synthesis and Characterization of Zwitterionic Polymer Brush Functionalized Hydrogels with Ionic Responsive Coefficient of Friction.

Freeze-thaw poly(vinyl alcohol) hydrogels (PVA-H) offer great potential for several biomedical applications due to their biomimetic mechanical properties and biocompatibility. Despite these advantages, the use of PVA-H for load bearing applications has been limited due to poor performance in boundary lubrication compared to natural tissue such as articular cartilage. Recently, zwitterionic polymer brushes have been shown to act as effective boundary lubricants on rigid substrates; however, to the best of our knowledge, the synergistic effects of zwitterionic brushes coupled with the biomimetic fluid load support exhibited by hydrogels have not been reported. We report here on our investigation involving the synthesis and characterization of two unique types of polymer brush functionalized PVA hydrogels. The zwitterionic polymers that were compared contained either [2-(methacryloyloxy)ethyl]dimethyl-3-sulfopropylammonium hydroxide, PMEDSAH, or 2-methacryloyloxyethylphosphorylcholine, PMPC, repeating units. Both hydrogels coated with zwitterionic polymers were found to be cytocompatible. We report further on micrometer-scale surface properties via water contact angle goniometry, surface roughness measurements, and scanning electron microscopy. Finally, the impact of brush functionalization on the mechanics of the tribologically enhanced gels is reported with comparison to natural articular cartilage within the context of Hertzian contact theory.

The use of a hydrogel implant in the repair of osteochondral defects of the knee: A biomechanical evaluation of restoration of native contact pressures in cadaver knees.

BACKGROUND: Osteochondral injuries have been treated by a variety of methods, each having its own drawbacks. The purpose of this study was to determine the biomechanical feasibility of using a hydrogel implant replacement for an osteochondral core defect. The hypothesis of this study was that the contact pressure of the native knee can be recreated with the use of a hydrogel implant. METHODS: Six cadaver knees were tested in a knee simulator while contact pressures were measured on the tibial plateau. Pressure data was collected in the intact knee, after coring of the condyle and after insertion of a hydrogel implant. Following 1000 gait cycles of fatigue testing, each knee was taken through axial loading indentation testing where the stiffness of the in situ implant was compared to the contralateral condyle. FINDINGS: While coring significantly reduced the peak pressure at the coring site from 1.8 MPa in the intact knee to 0.0 MPa after coring, implant insertion significantly increased it to 1.2 MPa. There was no significant difference in the peak pressures or the average pressures at the hole location between the intact knee and following implant insertion. After fatigue testing, no macroscopic loosening or implant damage was observed. Based on indentation testing, the stiffness of the medial condyle, 157 N/mm, was significantly less than the lateral condyle, 696 N/mm. INTERPRETATION: The insertion of the hydrogel implant was able to achieve restoration of contact pressures in the knee supporting the viability of hydrogel implants in the treatment of osteochondral lesions of the knee.

Synthesis and characterization of a zwitterionic hydrogel blend with low coefficient of friction.

Hydrogels display a great deal of potential for a wide variety of biomedical applications. Often times the performance of these biomimetic materials is limited due to inferior friction and wear properties. This manuscript presents a method inspired by the tribological phenomena observed in nature for enhancing the lubricious properties of poly(vinyl alcohol) (PVA) hydrogels. This was achieved by blending PVA with various amounts of zwitterionic polymer, poly([2-(methacryloyloxy) ethyl] dimethyl-(3-sulfopropyl) ammonium hydroxide) (pMEDSAH). Our results indicate that pMEDSAH acts as an effective boundary lubricant, allowing for reduction in coefficient of friction by more than 80%. This reduction in friction coefficient was achieved while maintaining comparable mechanical and physical properties to that of the neat material. Also, these zwitterionic blends were found to be cytocompatible. Analysis of the structure to property relationships within this system indicate that the zwitterionic polymer served as a boundary lubricant and promoted a reduction in friction through hydration lubrication. This novel approach provides a promising platform for further investigations enhancing the tribological properties of hydrogels for biomedical applications. STATEMENT OF SIGNIFICANCE: The novelty of this work stems from showing that zwitterionic polymers can be used as an extremely effective hydrogel boundary lubricant. This work will have significant scientific impact because to date, design of hydrogels has emphasized replication of mechanical properties, but in order for these types of materials to be fully utilized as biomaterials it is imperative that they possess improved tribological and lubrication properties, because ignoring the surface and boundary lubrication mechanism, make these potential load-bearing substitutes incompatible with other natural articulating surfaces, leading the constructs to wear, fail, and damage healthy tissue. Our work also provides unique insight to the structure-property-function relationships of these biomaterials which will be of great interest to the readership of the journal.