Oxidative damage to hyaluronate and glucose in synovial fluid during exercise of the inflamed rheumatoid joint. Detection of abnormal low-molecular-mass metabolites by proton-n.m.r. spectroscopy

Abstract

Proton Hahn spin-echo n.m.r. spectroscopy was employed to detect abnormal metabolites present in rheumatoid synovial fluid that are derived from the deleterious generation of reactive oxygen radical species during exercise of the inflamed rheumatoid joint. A resonance attributable to a low-molecular-mass N-acetylglucosamine-containing oligosaccharide formed by the oxygen-radical-mediated depolymerization of synovial-fluid hyaluronate was clearly demonstrable when subjects with inflammatory joint disease were exercised. Moreover, formate, which may be derived from the attack of OH.radical on synovial-fluid carbohydrates, was also readily detectable in these samples. gamma-Radiolysis of rheumatoid synovial fluid samples and aqueous solutions of hyaluronate also gave rise to the production of the low-molecular-mass hyaluronate-derived oligosaccharide species and markedly elevated concentrations of (non-protein-bound) formate in the biological fluids. As expected, corresponding spectra of gamma-irradiated blood serum samples obtained from normal volunteers did not contain the signal attributable to the low-molecular-mass oligosaccharide species, but the formate resonance (barely detectable in non-irradiated normal serum samples) became clearly visible. Additionally, a curious increase in the effective concentration of non-protein-bound low-molecular-mass metabolites such as acetate, citrate, lactate and glutamine was observed after gamma-radiolysis of all biological fluids studied. The hyaluronate-derived low-molecular-mass oligosaccharide species and formate are suggested as novel markers of reactive oxygen radical activity in the inflamed rheumatoid joint during exercise-induced hypoxic/reperfusion injury.

Free Radicals: Properties, Sources, Targets, and Their Implication in Various Diseases

“…Elevated levels of MDA, NO • , protein carbonyls, oxidized hyaluronic acid and oxidized LDL have been reported in RA patients [192][193][194][195]. These oxidized LDL can be ingested in large quantities by monocytes results in the formation of Foam cells that are present in atherosclerotic plaques of vessles and have also been found in RA synovial fluid [196].…”

Oxidant and anti‐oxidant systems of synovial fluid from patients with knee post‐traumatic arthritis

“…Prooxidant-anti-oxidant imbalance in PA may be due to the decreased synovial fluid viscosity. Tulamo et al 43 found that the SF concentration of hyaluonic acid can be used as a diagnostic marker for chronic PA. Takahasi et al 44 and Grootveld et al 21 found that exposition of hyaluronan on ROS, notably . OH, potentially results in decreased high molecular weight hyaluronan.…”

“…[21][22][23][24][25][26] However, we also suggested a simple scheme of the generation of individual ROS (Fig. 4).…”

Evaluation of efficacy of arthrocentesis (with normal saline) with or without sodium hyaluronate in treatment of internal derangement of TMJ – A prospective randomized study in 20 patients

“…Thus, the degraded form of hyaluronic acid indirectly affects the joint lubrication. 10 In the absence of lubricant, there is increased adhesiveness, friction, shear and rupture of articular surfaces.…”

“…Zero (0) in VAS scale means no pain (VAS I), no click (VAS II). Ten (10) in VAS scale means marked intense pain (VAS I), audible click (VAS II).…”