Electrochemical properties of ionic liquids (pyridinium and imidazolium salts) and the effect of additives of organic solvents on the electrochemical determination of organic compounds in ionic liquids have been studied. Transformations of aromatic and aliphatic sulfur compounds in ionic liquids in the presence of aromatic substrates are discussed. A new method has been proposed for identification of organic sulfur compounds–gas chromatography on columns with ionic liquid as the active phase.
Triarylantimony(V) catecholate complexes were synthesized by the oxidative addition of 3,6-di-tert-butyl-4,5-dimethoxy-o-benzoquinone to triarylstibines. The electrochemical properties and antiradical activity of the synthesized compounds were studied. According to cyclic viltammetry data, the complexes are oxidized via two consecutive quasi-reversible stages. Introduction of halogen atoms in para-position of phenyl groups at Sb(V) causes anodic shifts of the oxidation potentials and enhances stability of the mono- and dicationic forms of the compounds, which form in the course of electrochemical transformations. Triarylantimony(V) catecholate complexes exhibit appreciable antiradical activity in the auto-oxidation of oleic acid. In was found that the inhibitory activity of the complexes depends on their redox potential.
We consider the possible application of pyridinium ionic liquids to desulfurize hydrocarbon raw products and to transform the extracted toxic admixtures into promising sulfur compounds. Anodic oxidation of the extracted thiols as well as oxidation in the presence of electron mediators ( N,N,N′,N′ -tetramethyl-1,4-phenylenediamine, tri- p -bromophenylamine, and tri- p -tolylamine) leads to the corresponding disulfides.
Are researched antioxidant properties of pair-replaced phosphorus contain ionole derivatives in vitro and in vivo in comparison with analogue of vitamin E trolox. It is established, that the additive in feedstuff of aquatic organisms of researched compounds leads to increase in growth rate, level recession of accu-mulation the end products of lipids peroxidase oxidation in liver, membranes of blood erytrocytes, in-crease the catalase activity of blood erytrocytes hemolysate.
The synthetic analogues of natural porphyrins are widely used in medicine as pharmaceutical diagnostic markers. It was shown the possibility of applying porphyrins in the therapy of the diseases, connected with the development of oxidative stress. The paper presents the results of the study of antioxidant activity of the free base meso-tetrakis(3,5di-tert-butyl-4-hydroxyphenyl)porphyrin R 4 PH 2 , as well as non-substituted analogue - meso-tetraphenylporphyrin (TPPH 2 ) in the conditions of autooxidation and under promotion of oxidation by organotin compounds. The ability of the free base of porphyrin containing antioxidant 2,6-di-tert-butyl phenolic groups to decrease the oxidation by peroxide of lipids liver gomogenates, sturgeon sperm, fish feed has been studied. Accumulation of intermediate oxidation products from liver homogenates, sperm of the Russian sturgeon (Acipenser guldenstadti Brandt) as a stable complex with thiobarbituric acid (TBARS) and oxidation products from fish feed (hydroperoxides ROOH) was monitored by spectrophotometry and iodometric titration, respectively. The efficiency of antioxidative action (EAA) of studed porphyrins in each series of experiences with varying duration of lipids peroxidation in liver homogenates was calculated as EAA = [(C 0 -C 1 )/C 0 ]·100%, where C 1 is TBARS concentration in homogenates of liver containing the studied compounds and C 0 in a control experiment without additions. If the value of EAA factor was positive, it was considered that the testing material shows the antioxidative action; in the case of negative EAD factor it was considered that the testing material shows the prooxidative activity. The initial concentration of the studied compounds was 0,1 mM. In the model system the antioxidant activity of R 4 PH 2 in peroxidation of liver lipids remains almost constant in the wide interval of concentrations (0,01 - 10 mM). It was established that in the middle stages of the oxidation process (3 h, 24 h) the antioxidant action of TPPH 2 is inverted to the prooxidant. The presence of 2,6-ditert-butylphenolic groups in the free base porphyrin macrocycle results in an inhibitory effect. The introduction of the redox-active ion metal in the macrocycle reduces the inhibition effect of 2,6-di-tert-butylphenol fragments in oxidative destruction of liver lipids. The prooxidantive properties of TPPH 2 during the oxidive destruction of the lipids of fish fodder were observed. Addition of this porphyrin to lipid drawing from the fish fodder in the concentration 150 mg/ kg of fodder leads to an increase in the level the formation of primary oxidation products, namely, hydroperoxides ROOH. The organic derivatives of tin, acting as superecotoxicants, promote peroxidation of lipids in the drawing from the fish fodder. The greatest promoting effect of the lipid peroxidation was observed in the presence of СН 3 SnCl 3 . It was shown earlier that toxicity of heavy metals compounds could be connected with complexation of important bio dartboards as well as development of radical processes. So it is possible to use the active radicals traps as antidotes. With the aim of increasing of toxicoprotector efficiency, we offer to use compounds containing antioxidation part and complexating groups in molecule. Such compounds can be porphyrinic systems, but it is necessary to take into account the possibility of revealing of prooxidative properties by these compounds. It is discovered, that TPPH 2 strengthens the promoting influence of the methyl derivatives of tin on the level of accumulation of hydroperoxides in the lipid drawing from the fish fodder. Since the oxidative activity of TPPH 2 and R n SnCl 4-n are summed consequently the application of TPPH 2 for detoxication of R n SnCl 4-n is inadvisable. The promoting activity of organotin species in the presence of the porphyrin containing sterically-hindered phenolic moieties decreases significantly when compared with the activity of organotins alone. R 4 PH 2 was superior to the standard antioxidants α-tocopherol, 2,6-di(tert-butyl) phenols, 2,6-di(tert-butyl)-4-methylphenol (ionol).
We have analyzed the influence of the (tetraphenylporphyrin (TPP), 3,5-di-tret-butil-4-hydroxyphenylporphyrin (TPP-OH)) on carbonylic products accumulation identified with the help of thiobarbituric acid in the sperm of the Russian sturgeon (Acipenser gьldenstдdti Brandt) in vitro in the presence of Hg(NO3)2, CH3HgI, CdCl2 and (CH3)2SnCl2 in conditions of long running oxidation. It was shown the reduction of the rate of the peroxidation of lipids of sturgeon sperm in the presence of studied porphyrins under conditions of auto-oxidation and at promoting the process of heavy metals combination, that gives the possibility to use porphyrin systems as antioxidants. The greater efficiency of TPP-OH in comparison with TPP was observed at all stages of investigation both in conditions of auto-oxidation and in the presence of heavy metals compounds.