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The aim of the present study was to estimate the ability of individual phenolic acids to eliminate Fe(II) ions from the solution. Moreover, the influence of phenolic acids on the ferroxidase activity of ceruloplasmin (Cp) isolated from blood plasma of healthy volunteers (CpC) and patients with atherosclerosis obliterans (CpAO) was established in vitro. Phenolic acids demonstrated a ferroxidase-like activity, i.e. the ability to eliminate Fe(II) ions, within the studied concentration range of 2.0-17.0 mol 10-5 dm-3, in the following order of decreasing effectiveness: caffeic acid (CA)>ellagic acid (EA)>chlorogenic acid (ChA)>ferulic acid (FA) ≈ p-coumaric acid (PcA) = sinapic acid (SA). The study showed that the ability of phenolic acids to eliminate Fe(II) ions by oxidation or chelation was related to the structure of the former, to the presence of orto -OH groups, especially. Furthermore, the effect of the molar ratio of phenolic acid to Fe(II) ion was observed. EA and ChA, both containing two orto-OH groups and the highest number of –OH groups (4 and 5, respectively), demonstrated the greatest ability to eliminate Fe(II) ions, especially at the Fe(II) to phenolic acid molar ratio of 6:1. Phenolic acids added to samples with a constant amount of Cp caused decrease in the concentration of Fe(II) ions. Therefore, it may be assumed that the addition of phenolic acids to CpC and CpAO, even in low concentrations, caused a significant decrease in the concentration of Fe(II) ions.
Ceruloplasmin (Cp) is the major antioxidant in plasma, a protein that carries about 95% of the total copper. Multiple biochemical activities of ceruloplasmin have been described, including copper transport or oxidation of Fe(II) to Fe(III) for subsequent uptake by transferrin and ferritin. Reduction of the pool of free Fe(II) ions by Cp prevents the generation of free radicals and reactive oxygen species by oxidation of Fe(II), thus inhibiting the Haber-Weiss reaction. The removal of both free Fe(II) and Fe(III) ions from blood plasma by polyphenols enhances the antioxidant system of the living organism. However, the mechanism of interactions between exo- and endogenous antioxidants is still under consideration. The effect of raspberry seed extract (RSE) on the ferroxidase activity of ceruloplasmin isolated from plasma of patients with chronic arterial occlusion of the lower limbs due to atherosclerosis (CpAO) was investigated. Moreover, the effect of RSE on the ferroxidase activity of Cp isolated from healthy volunteers (CpC) was also estimated. The ferroxidase activity of Cp, expressed as ΔFe(II), was determined by spectrophotometry with the use of the Fe(II) – histidine complex and ferrozine as a chromogenic reagent. The addition of RSE to samples with the same amount of both CpAO or CpC in each caused an increase in ΔFe(II). The polyphenol-rich RSE may assist Cp in the fight against free radicals and reactive oxygen species when the disease occurs due to an excessive use or reduced production of endogenous antioxidants.
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