An electron spin resonance (ESR) technique is employed to determine the free radical distribution in the articulating surfaces of retrieved acetabular cups and knee-joint plateaus (retrieved after more than 6 years of implantation). Similar measurements made on samples prepared from cyclically stressed and unstressed cups, and on samples following oxidations in nitric acid and intralipid solutions provided sufficient data to gain more knowledge about the combined chemical and mechanical effects on PE free radicals during implantation. In UHMWPE free radicals are primarily initiated by gamma-ray sterilization; however, during implantation, peroxy (scission type) free radicals are formed and reach a maximum concentration level (equilibrium state) due to oxidation by chemical (hemoglobin and/or synovial fluids) environment of the joints. Subsequently, due to frictional heating and stress in the loading zones, free radical reaction is accelerated and their number is reduced only in those areas. This is consistent with the observations of a temperature rise in acetabular cups during in vitro frictional wear stress tests and in vivo telemetry observations, as reported by others. Compared with the previously reported SEM micrographs the low-free-radical regions are correlated with high-wear areas and the high-free-radical regions with the low-wear areas.
Solid-state electron paramagnetic resonance (EPR) spectroscopy of commercial samples of isolated soy proteins (ISP) revealed a symmetrical free-radical signal typical of carbon-centered radicals (g= 2.005) ranging from 2.96 x 10(14) to 6.42 x 10(14) spins/g. The level of free radicals in ISP was 14 times greater than similar radicals in sodium caseinate, 29 times greater than egg albumin, and about 100 times greater levels than casein. Nine soy protein powdered drink mixes contained similar types of free radicals up to 4.10 x 10(15) spins/g of drink mix, or up to 6.4 times greater than the highest free-radical content found in commercial ISP. ISP samples prepared in the laboratory contained trapped radicals similar to the levels in commercial ISP samples. When ISP was hydrated in 2.3 mM sodium erythorbate or 8.3 mM L-cysteine, frozen and dried, the level of trapped free radicals increased by about 17- and 19-fold, respectively. The ESR spectrum of defatted soybean flakes contained overlapping signals from the primary free-radical peak (g= 2.005) and a sextet pattern typical of manganese-II. The manganese signal was reduced in the laboratory ISP and very weak in the commercial ISP.
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