The effect of hyaluronic acid on the corrosion of an orthopedic CoCrMo-alloy in simulated inflammatory conditions

Abstract

During joint inflammation, various reactive oxygen species (ROS) are present in the surrounding tissue and joint fluid. In the laboratory, hydrogen peroxide (H 2 O 2) is typically used to simulate inflammatory conditions, and media containing proteins and hyaluronic acid (HA) are employed to simulate joint synovial fluid. Electrochemical interactions between H 2 O 2 and HA in the presence of a CoCrMo surface are expected, since HA molecules contain redox-active moieties. We hypothesized that any redox reactions of these moieties with ROS will mitigate the oxidizing effect of H 2 O 2 on the CoCrMo surface, limiting the corrosion rate of the metal. Non-destructive electrochemical measurements (open circuit potential, linear polarization resistance and electrochemical impedance spectroscopy) were used to investigate the corrosion response of CoCrMo in synovial model fluid containing physiologically relevant concentrations of albumin proteins and hyaluronic acid, with and without H 2 O 2. Two different molarities of H 2 O 2 , 3 mM and 30 mM, were tested. While both molarities are within physiological limits, 3mM is well within the range HA could mitigate, whereas 30 mM is not. Contrary to our hypothesis, HA did not alleviate corrosion in 3 mM H 2 O 2 and even caused a corrosion increase in the case of 30 mM H 2 O 2. The decrease in corrosion resistance of the alloy may be attributed to the complexation of degenerated HA molecular chains with chromium ions released from the metallic surface, which are necessary to build a protective oxide film. This finding has clinical implications, suggesting that HA accelerates corrosion of CoCrMo implants in the presence of strong inflammation.

Corrosion resistance of the nickel‐free high‐nitrogen steel FeCrMnMoN0.9 under simulated inflammatory conditions

“…The Chi‐squared values (squared sum of weighted residuals, also called Goodness of Fit) are in the order of magnitude of 1E‐04 – 1E‐05, documenting a good fit of the model circuit (the smaller the Chi‐squared value, the better the fit). The resistance of the bulk solution ( R S ~ 54 Ω cm 2 ) corresponds to the values found, under identical conditions, in a previous study 21 . At the outer interface, capacitive values ( Q OUT ) were generally higher in the presence of HA, suggesting adsorption of HA at this interface.…”

“…The protein and HA concentrations used in this study relate to the synovial fluid of patients after total hip replacement 20 . Details about the electrolyte preparation have been described earlier 21 …”

Synthetic periprosthetic synovial fluid development for in vitro cell‐tribocorrosion testing using the Taguchi array approach

“…Our group has previously reported that 1 mM H 2 O 2 in 1X PBS had a complete lethal effect on U937 cells cultured on CoCrMo discs (Shi, 2016), compared to the lowest viability achieved in this work with 1 mM H 2 O 2 in synthetic synovial fluid trials (55%). We hypothesize that H 2 O 2 had similar interactions with solution HA as previously reported (Radice et al, 2019), where HA redox‐active moieties mitigate the oxidizing effect of H 2 O 2 . GSH I / I O results suggest that the RAW 264.7 cells were effectively metabolizing ROS using GSH, with several high viability readings corresponding with larger GSH intensities.…”

“…Some of the major constituents of synovial fluid are not found in simple FBS solutions used for tribological testing yet have been proven to be significantly influential to the joint environment and implant functionality. For example, HA and metal ions directly impact inflammatory properties, surface‐solution interactions, and organometallic composite layer formation surrounding the artificial joint (Radice, Yao, Babauta, Laurent, & Wimmer, 2019). HA in addition to proteoglycans and proteins competitively adsorb to the surface of implants, contributing to a multilayer film composite on top of the metal‐oxide film and underneath a much thicker albumin‐phosphate layer (Muñoz & Mischler, 2007).…”

“…It has also been hypothesized that retrieved synovial fluid has electrochemical properties that differ drastically from FBS due to the effects of ROS. Hydrogen peroxide (H 2 O 2 ) in the presence of HA was theorized to reduce the redox activity of HA moieties, thus mitigating the oxidizing effects of ROS on CoCrMo alloy surfaces (Radice et al, 2019). It was found that the combination of the two factors either maintained or accelerated the corrosion rate of CoCrMo alloy at both concentrations of H 2 O 2 (3 mM, 30 mM).…”