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J Chromatogr B Analyt Technol Biomed Life Sci. 2009 Oct 15;877(28):3384-92. doi: 10.1016/j.jchromb.2009.03.035. Epub 2009 Mar 28.

Sulfenic acid--a key intermediate in albumin thiol oxidation.

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Laboratorio de EnzimologĂ­a, Facultad de Ciencias, Universidad de la RepĂșblica, Montevideo, Uruguay.


The single thiol of human serum albumin (HSA-SH) is the predominant plasma thiol. Both circulating albumin and pharmaceutical preparations are heterogeneous regarding the thiol redox status, as revealed by anion-exchange-hydrophobic interaction chromatography. Sulfenic acid (HSA-SOH) is an intermediate in HSA-SH oxidation processes that was detected through different techniques including mass spectrometry. Recently, quantitative data led to the determination of rate constants. The preferred fate of HSA-SOH is the formation of mixed disulfides. Alternatively, HSA-SOH can be further oxidized to sulfinic and sulfonic acids. Oxidized forms increase under disease conditions, underscoring the importance of HSA-SH as a plasma scavenger of intravascular oxidants. We here provide a critical review of the oxidation of HSA-SH in the context of the intravascular compartment, with emphasis in the methodological approaches of mass spectrometry and chromatography for the analysis of albumin thiol redox states.

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