NMR studies on human, pathologically changed synovial fluids: role of hypochlorous acid

Recently, it has been reported that hypochlorous acid (HOCl), a special product of neutrophil myeloperoxidase, degrades N-acetyl groups of N-acetylglucosamine, chondroitin sulfate, hyaluronic acid, and minced articular cartilage via a transient product to acetate. This work concerns 1H NMR investigations of synovial fluids of patients with rheumatoid arthritis (RA). Synovial fluids of patients with severe forms of this disease are characterized by enhanced 1H NMR signals for N-acetyl groups (approximately 2.0 ppm) and acetate (1.90 ppm) and the appearance of a broad but less intense signal at 2.35 ppm. It is likely that this signal corresponds to the transient, chlorinated product of degradation of N-acetyl groups by hypochlorous acid. Moreover, 1H NMR signal intensities of N-acetyl groups and acetate strongly correlate with the myeloperoxidase activities in synovial fluids from patients with rheumatoid arthritis. These results have been confirmed by treatment of native sheep synovial fluid with sodium hypochlorite, resulting in the formation of the same resonances as observed in pathologically changed synovial fluids from humans. Thus, it is concluded that HOCl plays an important role for the cartilage degradation during rheumatoid arthritis.