Busca avançada
Ano de início
Entree
(Referência obtida automaticamente do Web of Science, por meio da informação sobre o financiamento pela FAPESP e o número do processo correspondente, incluída na publicação pelos autores.)

Mass Spectrometry Characterization of Thiol Conjugates Linked to Polyoxygenated Polyunsaturated Fatty Acid Species

Texto completo
Autor(es):
Chaves-Filho, Adriano B. [1] ; Yoshinaga, Marcos Y. [1] ; Dantas, Lucas S. [1] ; Diniz, Larissa R. [1] ; Pinto, Isabella F. D. [1] ; Miyamoto, Sayuri [1]
Número total de Autores: 6
Afiliação do(s) autor(es):
[1] Univ Sao Paulo, Inst Quim, Dept Bioquim, BR-05508000 Sao Paulo, SP - Brazil
Número total de Afiliações: 1
Tipo de documento: Artigo Científico
Fonte: Chemical Research in Toxicology; v. 32, n. 10, p. 2028-2041, OCT 2019.
Citações Web of Science: 0
Resumo

Radical mediated oxidation of polyunsaturated fatty acids (PUFA) is known to generate a series of polyoxygenated cyclic products (PUFA-O-n, n >= 3). Here, we describe the characterization of glutathione (GSH) conjugates bound to polyoxygenated docosahexaenoic (DHA-O-n, n = 3-9), arachidonic (ARA-O-n, n = 3-7), a-linolenic (ALA-O-3), and linoleic (LA-O-3) acid species. Similar conjugates were also characterized for N-acetylcysteine (NAC) and Cu,Zn-superoxide dismutase (SOD1). Extensive LC-MS/MS characterization using a synthetic alpha-linolenic hydroxy-endoperoxide (ALA-O-3) derivative revealed at least two types of mechanisms leading to thiol adduction: a mechanism involving the nucleophilic attack by thiolate anion on 1,2-dioxolane to form a sulfenate ester-bonded conjugate and a mechanism involving cleavage of the dioxolane to form a alpha,beta-unsaturated carbonyl followed by the Michael addition reaction. Finally, we detected a GSH conjugate with hydroxy-endoperoxide derived from linoleic acid (LA-O-3) in mice liver. In summary, our study reveals the formation of a series of thiol conjugates that are bound to highly oxygenated PUFA species. GSH conjugates described in our study may potentially play relevant roles in redox and inflammatory processes, especially under high oxygen tension conditions. (AU)

Processo FAPESP: 13/07937-8 - Redoxoma
Beneficiário:Ohara Augusto
Modalidade de apoio: Auxílio à Pesquisa - Centros de Pesquisa, Inovação e Difusão - CEPIDs
Processo FAPESP: 10/50891-0 - Ácido docosahexaenóico e colesterol: caracterização e detecção de produtos de oxidação, modificação de proteínas e implicações na esclerose lateral amiotrófica
Beneficiário:Sayuri Miyamoto
Modalidade de apoio: Auxílio à Pesquisa - Regular