Radice S, Yao J, Babauta J, Laurent M P, Wimmer M A
Rush University Medical Center, Department of Orthopedic Surgery, 1611 W. Harrison Street, Chicago, IL 60612, USA.
University of Washington, Department of Orthopaedic Surgery and Sports Medicine, 401 Broadway, Seattle, WA 98122, USA.
Materialia (Oxf). 2019 Jun;6. doi: 10.1016/j.mtla.2019.100348. Epub 2019 May 10.
During joint inflammation, various reactive oxygen species (ROS) are present in the surrounding tissue and joint fluid. In the laboratory, hydrogen peroxide (HO) 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 HO 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 HO 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 HO. Two different molarities of HO, 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 HO and even caused a corrosion increase in the case of 30 mM HO. 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.
在关节炎症期间,周围组织和关节液中存在各种活性氧(ROS)。在实验室中,通常用过氧化氢(HO)来模拟炎症条件,并使用含有蛋白质和透明质酸(HA)的培养基来模拟关节滑液。由于HA分子含有氧化还原活性部分,预计在CoCrMo表面存在的情况下,HO与HA之间会发生电化学相互作用。我们假设这些部分与ROS的任何氧化还原反应将减轻HO对CoCrMo表面的氧化作用,限制金属的腐蚀速率。使用无损电化学测量(开路电位、线性极化电阻和电化学阻抗谱)来研究CoCrMo在含有生理相关浓度白蛋白和透明质酸的滑膜模型流体中,有无HO时的腐蚀响应。测试了两种不同摩尔浓度的HO,3 mM和30 mM。虽然这两种摩尔浓度都在生理范围内,但3 mM完全在HA可以减轻的范围内,而30 mM则不然。与我们的假设相反,HA在3 mM HO中并未减轻腐蚀,甚至在30 mM HO的情况下导致腐蚀增加。合金耐腐蚀性的降低可能归因于退化的HA分子链与从金属表面释放的铬离子的络合,而这些铬离子是形成保护性氧化膜所必需的。这一发现具有临床意义,表明在存在强烈炎症的情况下,HA会加速CoCrMo植入物的腐蚀。