Cis−Trans Isomerization of Polyunsaturated Fatty Acid Residues in Phospholipids Catalyzed by Thiyl Radicals

Ferreri, Carla; Costantino, Cristina; Perrotta, Laura; Landi, Laura; Mulazzani, Quinto G.; Chatgilialoglu, Chryssostomos

doi:10.1021/ja0040969

Cited by 118 publications

(173 citation statements)

References 39 publications

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“…The high efficiency of all-trans retinol and ascorbic acid as antiisomerising agents in the lipophilic and hydrophilic compartments, respectively, parallels the well-assessed high reactivity of RS • radicals towards these two antioxidants . Considering polyunsaturated substrates, the isomerization mechanism occurs as a step-by-step process depicted in Figure 6 for linoleate moiety, i.e., each isolated double bond behaves independently as discussed above (Ferreri et al, 2001). Chatgilialoglu & Ferreri, 2005).…”

Section: Oxidative Transformations Of Lipid Vesicles and The Antioxidmentioning

confidence: 99%

Biomimetic Chemistry: Radical Reactions in Vesicle Suspensions

Chatgilialoglu¹,

Ferreri²

2010

Biomimetics Learning From Nature

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Section: Oxidative Transformations Of Lipid Vesicles and The Antioxidmentioning

confidence: 99%

Biomimetic Chemistry: Radical Reactions in Vesicle Suspensions

Chatgilialoglu¹,

Ferreri²

2010

Biomimetics Learning From Nature

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“…Based on biomimetic models, mostly using 2-mercaptoethanol (MSH) as the thiol, the isomerization has been correlated to the formation of diffusible thiyl radical (RS•), which are able to move from the aqueous compartment and reach the hydrophobic lipid bilayer. [12][13][14][15] Recently, it has been shown that biologically relevant thiols (such as glutathione) are able to induce cis-trans isomerization of the double bonds in unsaturated fatty acids. 12,13,16,17 Among biological relevant sulfur species, hydrogen sulfide (H 2 S) is a natural occurring gas with interesting roles in nervous and cardiovascular systems and in pathological conditions such as inflammation.…”

Section: Introductionmentioning

confidence: 99%

“…[12][13][14][15] Recently, it has been shown that biologically relevant thiols (such as glutathione) are able to induce cis-trans isomerization of the double bonds in unsaturated fatty acids. 12,13,16,17 Among biological relevant sulfur species, hydrogen sulfide (H 2 S) is a natural occurring gas with interesting roles in nervous and cardiovascular systems and in pathological conditions such as inflammation. Chemically, the reactions of the simplest S-centered radicals formed from H 2 S were studied using liposomes as biomimetic model.…”

Section: Introductionmentioning

confidence: 99%

“…2,10,19 Based on the efficiency of the thiyl radicalcatalyzed cis-trans isomerization, it was demonstrated that trans-phospholipids could be also formed in vivo under cellular stress. [12][13][14] The protection of the cis geometry is crucial, owing to the importance of keeping favourable properties of cell membranes deriving from the fluidity contribution by the bent unsaturated lipid structures. 10,11 Using biomimetic models of cis-trans lipid isomerization, 5,6,10 we were interested in the protection of cis lipid geometry from thiyl radical attack by common antioxidants.…”

Section: Introductionmentioning

confidence: 99%

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Biomimetic chemistry on the protection of cis phospholipid from the thiyl radical isomerization by common antioxidants

Lykakis¹,

Ferreri²,

Chatgilialoglu³

2015

Arkivoc

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Dedicated to Prof. Michael Orfanopoulos on the occasion of his 67th birthday and retirement, and for being a splendid teacher, scientist and friend DOI: http://dx.doi.org/10.3998/ark.5550190.p008.984 AbstractIn this paper the evaluation of cis phospholipids geometry protection from the thiyl radical isomerization in the presence of common antioxidants is studied. Thus, large unilamellar vesicles (LUVs) of glycerophospholipids containing oleate moieties were used as biomimetic model to demonstrate that hydrophilic ascorbic acid and urate, and hydrophobic all-trans retinol acetate and α-tocopherol, are able to inhibit cis-trans isomerization from the thiyl radicals that are known to react as efficient isomerizing species. The synergistic effect obtained by a mix of the hydrophilic and hydrophobic antioxidants at in vivo concentrations is also proved to exert an extraordinary protection for the integrity of cis lipid geometry.

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“…It is likely that thiyl radicals can effectively oxidize polyunsaturated fatty acids (PUFA) via abstraction of bis-allylic hydrogens, yielding pentadienyl radicals (8) with the subsequent formation of conjugated dienes, thiol-fatty acid adducts, and hydroperoxides (9,10). In addition, thiyl radicals can catalytically accelerate cis-trans isomerization of polyunsaturated fatty acid residues in phospholipids (9,10).…”

mentioning

confidence: 99%

Glutathione Propagates Oxidative Stress Triggered by Myeloperoxidase in HL-60 Cells

Borisenko

Martin

Zhao

et al. 2004

Journal of Biological Chemistry

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Glutathione acts as a universal scavenger of free radicals at the expense of the formation of the glutathionyl radicals (GS ⅐ ). Here we demonstrated that GS ⅐ radicals specifically interact with a reporter molecule, paramagnetic and non-fluorescent 4-((9-acridinecarbonyl)-amino)-2,2,6,6-tetramethylpiperidine-1-oxyl (Ac-Tempo), and convert it into a non-paramagnetic fluorescent product, identified as 4-((9-acridinecarbonyl)amino)-2,2,6,6-tetramethylpiperidine (Ac-piperidine). Horseradish peroxidase-, myeloperoxidase-, and cyclooxygenasecatalyzed oxidation of phenol in the presence of H 2 O 2 and GSH caused the generation of phenoxyl radicals and GS ⅐ radicals, of which only the latter reacted with Ac-Tempo. Oxidation of several other phenolic compounds (e.g. etoposide and tyrosine) was accompanied by the formation of GS ⅐ radicals along with a characteristic fluorescence response from Ac-Tempo. In myeloperoxidase-rich HL-60 cells treated with H 2 O 2 and phenol, fluorescence microscopic imaging of Ac-Tempo revealed the production of GS ⅐ radicals. A thiol-blocking reagent, N-ethylmaleimide, as well as myeloperoxidase inhibitors (succinyl acetone and azide), blocked formation of fluorescent acridine-piperidine. H 2 O 2 /phenolinduced peroxidation of major classes of phospholipids in HL-60 cells was completely inhibited by Ac-Tempo, indicating that GS ⅐ radicals were responsible for phospholipid peroxidation. Thus, GSH, commonly viewed as a universal free radical scavenger and major intracellular antioxidant, acts as a pro-oxidant during myeloperoxidase-catalyzed metabolism of phenol in HL-60 cells.Thiols are said to fulfill important antioxidant functions in cells and biological fluids. In particular, glutathione, the most abundant intracellular low molecular weight thiol, regulates the content of H 2 O 2 and organic (lipid) hydroperoxides via glutathione peroxidase-catalyzed reactions. GSH is also commonly presumed to act as a universal free radical sink toward a wide variety of different types of free radicals (1-5). Although scavenging of reactive radicals by GSH is believed to be an important antioxidant function of the latter, it may render effective protection only if the sulfur-centered glutathionyl radicals (GS ⅐ ) 1 formed in the scavenging reactions do not further propagate free radical generation. On the contrary, pro-oxidant activity of GSH should be expected if GS ⅐ radicals are reactive enough to interact with and cause damage to vital intracellular molecules.In fact, experiments in model systems indicate that GS ⅐ radicals can abstract hydrogen atoms from carbohydrates such as 2-deoxy-D-ribose and initiate irreversible DNA damage (6). Thiyl radicals are also capable of hydrogen abstraction from ␣-amino C-H bonds of amino acids with the consequent formation of carbon-centered radicals (7). However, reactions of thiyl radicals with carbohydrates and amino acids are reversible; moreover, carbon-centered radicals of carbohydrates and amino acids are stronger oxidants than thiyl radicals, suggesting tha...

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Cis−Trans Isomerization of Polyunsaturated Fatty Acid Residues in Phospholipids Catalyzed by Thiyl Radicals

Cited by 118 publications

References 39 publications

Biomimetic Chemistry: Radical Reactions in Vesicle Suspensions

Biomimetic Chemistry: Radical Reactions in Vesicle Suspensions

Biomimetic chemistry on the protection of cis phospholipid from the thiyl radical isomerization by common antioxidants

Glutathione Propagates Oxidative Stress Triggered by Myeloperoxidase in HL-60 Cells

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