RESUMO
In this work, using the example of model compounds, we studied the reactions resulting from the interaction of OH radicals with the hydrophilic part of sphingolipids. We compared the stopped-flow EPR spectroscopy and pulse radiolysis with optical detection methods to characterize radical intermediates formed in the reaction of OH radicals with glycerol, serinol and N-boc-serinol. Quantum chemical calculations were also performed to help interpret the observed experimental data. It was shown that H-abstraction from the terminal carbon atom is the main process that is realized for all the studied compounds. The presence of the unsubstituted amino group (-NH2) is seen to completely change the reaction properties of serinol in comparison with those observed in glycerol and N-boc serinol.
Assuntos
Glicerol/química , Radical Hidroxila/química , Propanolaminas/química , Propilenoglicóis/química , Teoria da Densidade Funcional , Espectroscopia de Ressonância de Spin Eletrônica , Interações Hidrofóbicas e Hidrofílicas , Modelos Químicos , Estrutura Molecular , Radiólise de Impulso , Esfingolipídeos/químicaRESUMO
Cytochrome c (cyt c) is a small hemoprotein involved in electron shuttling in the mitochondrial respiratory chain and is now also recognized as an important mediator of apoptotic cell death. Its role in inducing programmed cell death is closely associated with the formation of a complex with the mitochondrion-specific phospholipid cardiolipin (CL), leading to a gain of peroxidase activity. However, the molecular mechanisms behind this gain and eventual cyt c autoinactivation via its release from mitochondrial membranes remain largely unknown. Here, we examined the kinetics of the H2O2-mediated peroxidase activity of cyt c both in the presence and absence of tetraoleoyl cardiolipin (TOCL)- and tetralinoleoyl cardiolipin (TLCL)-containing liposomes to evaluate the role of cyt c-CL complex formation in the induction and stimulation of cyt c peroxidase activity. Moreover, we examined peroxide-mediated cyt c heme degradation to gain insights into the mechanisms by which cyt c self-limits its peroxidase activity. Bottom-up proteomics revealed >50 oxidative modifications on cyt c upon peroxide reduction. Of note, one of these by-products was the Tyr-based "cofactor" trihydroxyphenylalanine quinone (TPQ) capable of inducing deamination of Lys ϵ-amino groups and formation of the carbonylated product aminoadipic semialdehyde. In view of these results, we propose that autoinduced carbonylation, and thus removal of a positive charge in Lys, abrogates binding of cyt c to negatively charged CL. The proposed mechanism may be responsible for release of cyt c from mitochondrial membranes and ensuing inactivation of its peroxidase activity.
Assuntos
Cardiolipinas/química , Citocromos c/química , Peróxido de Hidrogênio/química , Carbonilação Proteica , Animais , Bovinos , Peroxidase do Rábano Silvestre/química , Lipossomos , OxirreduçãoRESUMO
The enrichment of flaxseed oil, which is a valuable plant source of PUFA omega-3, fat-soluble vitamins and other biologically active substances (BAS), makes it possible to strengthen the therapeutic and prophylactic effect of flaxseed oil. The study of the effect of BAS additives on the oxidative stability of flaxseed oil is an important step in the process of creating products based on enriched flaxseed oil. Experiments were conducted to investigate the influence of added BAS (coenzyme Q10, ß-carotene, lutein, zeaxanthin, α-tocopherol, α-tocopherol acetate, cholecalciferol, selenomethionine) on flaxseed oil oxidation stability. Kinetic data on accumulation of primary and secondary oxidation products, free fatty acids in flaxseed oil, as well as the consumption of BAS added to the oil during its storage, were obtained. Experimental results showed that the BAS could have both antioxidant and pro-oxidant properties depending on their chemical structure and concentration. Coenzyme Q10, carotenoids and selenomethionine at concentrations higher than 100, 10 and 0.5 mg/100 g respectively, accelerate significantly (p < 0.05) the oxidation of flaxseed oil. An addition of 5 mg/100 g ß-carotene inhibits formation of flaxseed oil oxidation products. The co-influence of synthetic and natural oxidation inhibitors with BAS on oxidative stability of flaxseed oil was studied. The fat-soluble esters of ascorbic acid and their compositions with natural antioxidants based on beans and soybeans appeared to be effective and safe stabilizers of flaxseed oil enriched with BAS. Resulting from the studies, new oxidation-resistant functional food products based on flaxseed oil are launched into manufacturing.
RESUMO
2-Hexadecenal (2HD) formation in the organism occurs via irreversible enzymatic degradation of sphingosine-1-phosphate or nonenzymatic γ-, UV-, or HOCl-induced destruction of a number of sphingolipids including S1P. The current research focuses on the study of 2HD effects on C6 glioma cells growth. The results obtained show that 2HD causes a dose-dependent decrease in proliferative and mitotic indices. The change in the mitotic index is due to the redistribution of cells in the different phases of mitosis. These processes are accompanied by cytoskeleton rearrangement and changes in cell morphology, which are expressed in F-actin redistribution, change in the number and type of filopodia and fibrils, leading to cell shape changes, decrease in intercellular contacts and monolayer rarefaction. Cells treatment with 2HD leads to apoptosis induction and signalling pathways modification, including activation of JNK, p38, and ERK1/2 MAPK but not PI3K. The effects observed are not related to the cytotoxicity of 2HD. Significance of the study: 2HD-an unsaturated aldehyde, which level can rise under conditions of oxidative stress as a result of nonenzymatic sphingolipids' destruction. The mechanisms of 2HD action on various cell types have not been sufficiently studied. Therefore, the study on functional role of this aldehyde in different cell types that may be its target is relevant. This study demonstrated that 2HD inhibits growth of C6 glioma cells due to modification of intracellular processes of signal transduction, cytoskeleton rearrangement, change in the mitotic regimen and apoptosis induction.
Assuntos
Aldeídos/farmacologia , Glioma/patologia , Animais , Apoptose/efeitos dos fármacos , Proliferação de Células/efeitos dos fármacos , Sobrevivência Celular/efeitos dos fármacos , Relação Dose-Resposta a Droga , Ratos , Relação Estrutura-Atividade , Células Tumorais CultivadasRESUMO
The interaction of reactive oxygen species with cell membrane lipids is usually considered in the context of lipid peroxidation in the nonpolar component of the membrane. In this work, for the first time, data were obtained indicating that damage to human cell membranes can occur in the polar part of lysophospholipids at the interface with the aqueous environment due to free radical fragmentation (FRF) processes. FRF products, namely 1-hexadecanoyloxyacetone (PAc) and 1-octadecanoyloxyacetone (SAc), were identified in human serum, and a GC-MS method was developed to quantify PAc and SAc. The content of FRF products in serum samples of 52 healthy donors was found to be in the range of 1.98-4.75 µmol/L. A linear regression equation, CPAc&SAc (µmol/L) = 0.51 + 0.064 × years, was derived to describe the relationship between age and content of FRF products. In 70 patients with acute surgical pathology in comparison with the control group of healthy donors, two distinct clusters with different concentration levels of FRF products were revealed. The first cluster: groups of 43 patients with various localized inflammatory-destructive lesions of hollow organ walls and bacterial translocation (septic inflammation) of abdominal cavity organs. These patients showed a 1.5-1.9-fold (p = 0.012) decrease in the total concentration of PAc and SAc in serum. In the second cluster: groups of 27 patients with ischemia-reperfusion tissue damage (aseptic inflammation), - a statistically significant increase in the concentration of FRF products was observed: in 2.2-4.0 times (p = 0.0001). The obtained data allow us to further understand the role of free-radical processes in the damage of lipid molecules. FRF products can potentially be used as markers of the degree of free-radical damage of hydroxyl containing phospholipids.
RESUMO
2-Hexadecenal (2-HD)-a biologically active long-chain fatty aldehyde formed in organism enzymatically or nonenzymatically in the reaction of free-radical destruction of sphingolipids under the action of hypochlorous acid, producing by myeloperoxidase. This research aimed to study 2-HD effects on polymorphonuclear leukocytes' (PMNLs) functions. It has been shown that at submicromolar concentrations, 2-HD causes an elevation in ROS production by PMNLs. It has been found that such effect is associated with signal transduction pathways modification and expressed in elevation of NADPH oxidase, MPO, and JNK-MAPK contributions to this process. At higher concentrations, 2-HD induces apoptosis, which correlates with a significant increase in free Ca2+ in the cytoplasm, a decrease in ROS production, and a decline in mitochondrial potential. Both of these processes are accompanied by cytoskeleton reorganization.
Assuntos
Apoptose , Neutrófilos , Neutrófilos/metabolismo , Espécies Reativas de Oxigênio/metabolismo , NADPH Oxidases/metabolismoRESUMO
The ability of ascorbic acid and a number of its derivatives to suppress replication of Herpes simplex virus type I was investigated in human rhabdomyosarcoma cell line. In parallel, interaction of the test compounds with carbon- and oxygen-centered radicals formed on radiolysis of hydroxyl-containing organic compounds was studied using the steady state radiolysis method. It has been shown that 2-O-glycoside of ascorbic acid, displaying marked antiviral properties against Herpes simplex virus type I, is also capable of inhibiting fragmentation and recombination reactions of α-hydroxyl-containing carbon-centered radicals while not affecting processes involving oxygen-centered radicals.
Assuntos
Antivirais/síntese química , Ácido Ascórbico/síntese química , Sequestradores de Radicais Livres/síntese química , Herpesvirus Humano 1/efeitos dos fármacos , Espécies Reativas de Oxigênio/metabolismo , Antivirais/farmacologia , Ácido Ascórbico/análogos & derivados , Ácido Ascórbico/farmacologia , Carbono/química , Linhagem Celular Tumoral , Sequestradores de Radicais Livres/farmacologia , Humanos , Oxigênio/química , Radiação Ionizante , Espécies Reativas de Oxigênio/efeitos da radiação , RabdomiossarcomaRESUMO
Linseed oil (LO) is known for its exceptional nutritional value due to the high content of alpha-linolenic acid (ALA), an essential omega-3 polyunsaturated fatty acid; its anticarcinogenic effect has been established in several experimental and epidemiological studies. As an adjuvant of chemotherapeutic agents, LO and other ALA-rich vegetable oils have been studied in only a handful of studies at the experimental level. However, the efficacy of antitumoral therapy using doxorubicin (Dox) in combination with ALA and ALA-rich substrates has not yet been investigated. In this work, the antitumor activity of LO in a wide dose range was studied with monotherapy and combined with Dox in animal models with Pliss lymphosarcoma (PLS) and Lewis lung adenocarcinoma (LLC). It was founded the daily oral administration of LO (1, 3, and 10 ml per 1 kg) to rats (PLS) and 6 ml/kg to mice (LLC) for 11-12 days from 7 days after subcutaneous transplantation of tumors has a stable statistically significant effect on the dynamics of tumor growth, reducing the intensity of tumor growth and increasing the frequency of complete tumor regressions (CR) compared with the control. LO showed high antimetastatic activity in the LLC model. Furthermore, LO at a dose of 3 ml/kg potentiates the antitumor effect of Dox in the PLS model, reducing the volume of tumors at the end of treatment by 2.0 times (p = 0.013), the value of the tumor growth index by 1.6 times (p < 0.03) and increasing the frequency of CR 60 days after the start of therapy by 3.5 times (p = 0.019) compared with the use of Dox alone. The combination of Dox and LO or fish oil allows growing efficiency therapy of LLC in comparison with Dox alone, increasing the frequency of CR to 73.68% and 94.4%, respectively, and reducing the frequency of metastasis to zero.
RESUMO
It has been shown that the development of coronavirus infection (COVID-19), especially in severe cases, is accompanied by hypoxia as a result of several pathological processes: alveolar blood supply disorders, hemolysis, COVID-associated coagulopathy. Under these conditions, the level of reactive oxygen species is increased and it is more likely that free-radical damage to biomolecules is caused by the process of free-radical fragmentation than oxidation. In contrast to the oxidation process, free-radical fragmentation reactions are more effectively inhibited by oxidizing agents than reducing agents. Therefore, the use of substances possessing both reducing and oxidizing properties, such as natural and synthetic quinones, bioflavonoids, curcuminoids, should reduce the probability of biomolecule destruction by oxidation as well as free-radical fragmentation processes.HighlightsCOVID-19 is accompanied by the iron release from the heme and «silent¼ hypoxiaROS initiate fragmentation reactions of biomolecules under conditions of hypoxiaBlocking of fragmentation process by oxidizers may lead to mitigation of COVID-19.
Assuntos
COVID-19/metabolismo , Radicais Livres/metabolismo , SARS-CoV-2/metabolismo , COVID-19/patologia , COVID-19/virologia , Radicais Livres/efeitos adversos , Heme/metabolismo , Humanos , Ferro/metabolismo , Oxirredução/efeitos dos fármacos , Espécies Reativas de Oxigênio/efeitos adversos , Espécies Reativas de Oxigênio/metabolismo , SARS-CoV-2/patogenicidadeRESUMO
Vicinal diols and its derivatives can be exploited as model compounds for the investigation of radiation-induced free-radical transformations of hydroxyl-containing biomolecules such as carbohydrates, phospholipids, ribonucleotides, amino acids, and peptides. In this paper, for the first time, the prospects of isotope reinforcement approach in inhibiting free-radical transformations of hydroxyl-containing compounds in aqueous solutions are investigated on the example of radiolysis of 1,2-propanediol and 1,2-propanediol-2-d1 aqueous solutions. At an absorbed dose rate of 0.110 ± 0.003 Gy·s-1 a profound kinetic isotope effect (KIE) is observed for the non-branched chain formation of acetone, which is a final dehydration product of predominant carbon-centred radicals CH3·C(OH)CH2OH. In 0.1 and 1 M deaerated solutions at pH 7.00 ± 0.01, the values of KIE are 8.9 ± 1.7 and 15.3 ± 3.1, respectively. A rationale for the fact that a strong KIE takes place only in the case of chain processes, which may occur during free-radical transformations of vicinal diols, is also provided herein based on the results of 2-propanol and 2-propanol-2-d1 indirect radiolysis. Lastly, the lack of KIE is shown in the case of 2-butanone formation from 2,3-butanediol or 2,3-butanediol-2,3-d2. This indicates that the type (primary, secondary) of the ß-carbonyl radicals formed as a result of CH3·C(OH)CH(OH)R (R = H, CH3) dehydration determines the manifestation of the effect.
Assuntos
Radical Hidroxila/química , Isótopos/química , Humanos , CinéticaRESUMO
This review presents data showing the possibility of novel pathways to be realized for free-radical transformations of glycerophospholipids and sphingolipids. These transformations include the stages of formation and subsequent decay of carbon- and nitrogen-centered radicals of the starting lipids resulting in the accumulation of signal molecules. The presence of a hydroxyl group in the polar component of lipids is a prerequisite for the implementation of these processes. This enables their structural modification and/or destruction to take place with the accumulation of biologically active products such as phosphatidic acid, ceramides, diacylglycerols and acylamides. Sphingolipids containing a free amino group, when interacting with active species of oxygen or chlorine, form aminyl radicals. These lipid radicals undergo further fragmentation, leading to the accumulation of 2-hexadecenal, which has a broad spectrum of biological activity. The presence of an amide group in the structure of sphingolipids determines the possibility of their photodestruction, which also results in the formation of 2-hexadecenal. In contrast with lipid peroxidation, which is inhibited by reducing agents, free-radical fragmentation reactions of hydroxyl-containing lipids involving carbon-centered radicals are blocked by oxidants.
Assuntos
Glicerofosfolipídeos/metabolismo , Oxigênio , Espécies Reativas de Oxigênio/metabolismo , Esfingolipídeos/metabolismo , Radicais Livres/química , Radicais Livres/metabolismo , Glicerofosfolipídeos/química , Humanos , Estrutura Molecular , Oxigênio/metabolismo , Esfingolipídeos/químicaRESUMO
The review summarizes and critically discusses data on biochemical and free-radical transformations of glycerophospholipids. The results presented therein demonstrate that hydroxyl-containing glycerophospholipids, such as cardiolipin, lyso-lipids and others, can undergo fragmentation upon interaction with radical agents forming the biologically active products. Hydrolysis of glycerophospholipids catalyzed by different phospholipases was shown to yield compounds, which can be involved in the free-radical fragmentation leading to significant changes in structures of original lipids.
Assuntos
Glicerofosfolipídeos/química , Peróxidos Lipídicos/química , Lipoxigenases/química , Lisofosfolipídeos/química , Fosfolipases/química , Animais , Antioxidantes/química , Antioxidantes/farmacologia , Biocatálise , Inibidores Enzimáticos/química , Inibidores Enzimáticos/farmacologia , Glicerofosfolipídeos/metabolismo , Humanos , Hidrólise , Peroxidação de Lipídeos/efeitos dos fármacos , Peróxidos Lipídicos/metabolismo , Lipoxigenases/metabolismo , Lisofosfolipídeos/metabolismo , Fosfolipases/antagonistas & inibidores , Fosfolipases/metabolismo , Plantas/química , Plantas/metabolismo , Quinonas/química , Quinonas/farmacologiaRESUMO
Effects of quinones and azoles on the formation of steady-state radiolysis products in aqueous solutions of glycerol-1-phosphate and aqueous dispersions of 1,2-dimyristoyl-glycero-3-phosphatidyl-glycerol has been investigated. The data obtained by LC-MS-ESI and spectrophotometric measurements shows that the compounds having quinoid structures, including the antitumor agent doxorubicin, and azoles having nitro groups effectively inhibit free-radical fragmentation of glycerol-1-phosphate and 1,2-dimyristoyl-glycero-3-phosphatidyl-glycerol, decreasing the radiation-chemical yields of either inorganic phosphate or phosphatidic acid respectively. The observed effects of blocking free-radical processes are believed to be related to the ability of the tested compounds to oxidize α-hydroxyl-containing carbon-centered radicals of starting substrates, which give rise to fragmentation reaction. The possibility of using the discovered properties of quinones, doxorubicin and nitroazoles to provide practical solutions in oncological radiotherapy and pathophysiology is discussed.
Assuntos
Azóis/química , Glicerofosfatos/química , Nitrocompostos/química , Fosfatidilgliceróis/química , Quinonas/química , Radicais Livres/síntese química , Radicais Livres/química , Estrutura MolecularRESUMO
Mitochondria are an important intracellular source of ROS as well as a sensitive target for oxidative damage under certain pathological conditions such as iron or copper overload. Mitochondrial membranes are rich in the tetraacyl phospholipid cardiolipin. Its integrity is important for efficient oxidative phosphorylation. Mouse liver mitochondria were subjected to oxidative stress by the Cu(2+)(Fe(2+))/H(2)O(2)/ascorbate system. Phosphatidic acid was detected in oxidized mitochondria, but not in unperturbed mitochondria. The Cu(2+)/H(2)O(2)/and (or not) ascorbate system caused the formation of phosphatidic acid and phosphatidylhydroxyacetone in cardiolipin liposomes. These products proceed via an HO*-radical induced fragmentation taking place in the polar moiety of cardiolipin. Mass spectrometry analysis of phosphatidic acid newly formed in mitochondria revealed that it has been derived from fragmentation of cardiolipin. Thus, free-radical fragmentation of cardiolipin in its polar part with the formation of phosphatidic acid is a likely mechanism that damages mitochondria under conditions of oxidative stress.
Assuntos
Mitocôndrias Hepáticas/metabolismo , Ácidos Fosfatídicos/biossíntese , Animais , Fenômenos Biofísicos , Cardiolipinas/metabolismo , Cromatografia Líquida de Alta Pressão , Feminino , Técnicas In Vitro , Ferro/toxicidade , Lipossomos , Metais/toxicidade , Camundongos , Camundongos Endogâmicos C57BL , Mitocôndrias Hepáticas/efeitos dos fármacos , Estresse Oxidativo , Espécies Reativas de Oxigênio/metabolismo , Espectrometria de Massas por Ionização e Dessorção a Laser Assistida por MatrizRESUMO
Co(II) and Ni(II) complexes with 4,6-di-tert-butyl-3-[(2-hydroxyethyl)thio]benzene-1,2-diol (L) have been synthesized and characterized by means of elemental analysis, TG/DTA, FT-IR, ESR, UV-vis, XRD, magnetic susceptibility, cyclic voltammetry and conductance measurements. According to the data obtained the organic compound acts as a bidentate O,S-coordinated ligand and yields Co(II) and Ni(II) complexes of the stoichiometry ML(2) which is characterized by square planar geometry. Antifungal and anti-HIV activities of the ligand and its metal(II) complexes were found to decrease in the sequence CuL(2)>CoL(2) ~ NiL(2)>HL, along with their reducing ability (determined electrochemically).
Assuntos
Fármacos Anti-HIV/química , Fármacos Anti-HIV/farmacologia , Antifúngicos/química , Antifúngicos/farmacologia , Metais/química , Compostos Organometálicos/química , Compostos Organometálicos/farmacologia , Compostos Organometálicos/síntese química , Análise Espectral/métodosRESUMO
Effects of ascorbic acid (AA), ascorbic acid glycoside (AAG) and alpha-tocopherol monoglycoside (TMG) on radiation - and H(2)O(2)-induced decomposition of thymine in aqueous solutions were investigated. Of the three compounds studied, AAG was found to possess the most marked protector properties. An explanation of this phenomenon has been given in terms of differences in molecular structures of AA and AAG, as well as properties of radical adducts formed during their interaction with OH radicals.
Assuntos
Glicosídeos/química , Peróxido de Hidrogênio/química , Timina/química , Timina/efeitos da radiação , Vitaminas/química , Água/química , Relação Dose-Resposta à Radiação , Doses de Radiação , SoluçõesRESUMO
The aim of this work was to compare cell form, size and volume as well as the locomotor activity of polymorphonuclear leukocytes (PMNLs) stimulated by adhesion to glass and exposed to hypochlorous acid at non-toxic dose. After 20min of adhesion to a glass surface, volume, cell surface area and projection area of PMNLs were equaled to 143.1±21.4µm3, 288.8±28.8µm2 and 248.3±32.3µm2, respectively. Projection area of PMNLs exposed to NaOCl was noticeably enlarged as compared with control samples. The cell volume of 20min adherent cells exposed to NaOCl was enlarged in comparison with both control cells and 5min adhered exposed to NaOCl cells. NaOCl exposure induced a degranulation of PMNLs as measured by lysozyme release. Granules could be found both above the cell surface and on the substratum near the cell. The S/V ratio for PMNLs increased (from 1.52 to 2.02µm-1) with the increasing of cell activation time. But at NaOCl addition the reverse tendency was observed (from 2.10 to 1.87µm-1). In cells exposed to NaOCl the redistribution and decrease of concentration of F-actin took place. This observation supports the hypothesis that the priming of PMNLs with hypochlorous acid modifies cell motility and morphology and reflects also on other functions.
Assuntos
Adesão Celular/efeitos dos fármacos , Adesão Celular/fisiologia , Ácido Hipocloroso/farmacologia , Neutrófilos/efeitos dos fármacos , Neutrófilos/fisiologia , Actinas/metabolismo , Tamanho Celular/efeitos dos fármacos , Humanos , Muramidase/metabolismo , Neutrófilos/metabolismoRESUMO
Effects of vitamins B, C, E, K and P, as well as coenzymes Q, on formation of final products of radiation-induced free-radical transformations of ethanol, ethylene glycol, alpha-methylglycoside and glucose in aqueous solutions were studied. Based on the obtained results, it can be concluded that there are substances among vitamins and coenzymes that effectively interact with alpha-hydroxyl-containing radicals. In the presence of these substances, recombination reactions of alpha-hydroxyalkyl radicals and fragmentation of alpha-hydroxy-beta-substituted organic radicals are suppressed. It has been established that the observed effects are due to the ability of the vitamins and coenzymes under study to either oxidize alpha-hydroxyl-containing radicals yielding the respective carbonyl compounds or reduce them into the initial molecules.
Assuntos
Álcoois/química , Ubiquinona/química , Vitaminas/química , Ácido Ascórbico/química , Etanol/química , Etilenoglicol/química , Glucose/química , Radical Hidroxila/química , Metilglicosídeos/química , Oxirredução , Complexo Vitamínico B/química , Vitamina E/química , Vitamina K/químicaRESUMO
Analysis of final products of radiation-induced transformations of galactocerebrosides (GalCer) in aqueous dispersions has been performed using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) and its combination of thin-layer chromatography (TLC). Ceramides were found to be the main products of GalCer gamma-radiolysis. From experimental results obtained in this study, as well as from the data available in the literature, an inference is made that the formation of ceramides occurs owing to fragmentation of radicals with an unpaired electron of the C2 atom of the carbohydrate moiety, formed from the starting compounds.
Assuntos
Radicais Livres/química , Galactosilceramidas/química , Espectrometria de Massas por Ionização e Dessorção a Laser Assistida por Matriz/métodos , Química Encefálica , Cromatografia em Camada FinaRESUMO
It has been shown using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) and its combination with thin-layer chromatography (TLC) that the action of the ascorbate/Fe(2+)/H(2)O(2) oxidizing system on cardiolipin and galactocerebroside results in the formation of phosphatidic acid (PA) and ceramide (Cer), respectively. These data, when combined with results obtained on radiolysis of similar substances, allowed the conclusion that the formation of PA and Cer occurs via an OH-induced fragmentation taking place in polar moiety of the starting substrates.