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      Improved analysis of malondialdehyde in human body fluids

      , , ,
      Free Radical Biology and Medicine
      Elsevier BV

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          Malondialdehyde and thiobarbituric acid-reactivity as diagnostic indices of lipid peroxidation and peroxidative tissue injury

          Increasing appreciation of the causative role of oxidative injury in many disease states places great importance on the reliable assessment of lipid peroxidation. Malondialdehyde (MDA) is one of several low-molecular-weight end products formed via the decomposition of certain primary and secondary lipid peroxidation products. At low pH and elevated temperature, MDA readily participates in nucleophilic addition reaction with 2-thiobarbituric acid (TBA), generating a red, fluorescent 1:2 MDA:TBA adduct. These facts, along with the availability of facile and sensitive methods to quantify MDA (as the free aldehyde or its TBA derivative), have led to the routine use of MDA determination and, particularly, the "TBA test" to detect and quantify lipid peroxidation in a wide array of sample types. However, MDA itself participates in reactions with molecules other than TBA and is a catabolic substrate. Only certain lipid peroxidation products generate MDA (invariably with low yields), and MDA is neither the sole end product of fatty peroxide formation and decomposition nor a substance generated exclusively through lipid peroxidation. Many factors (e.g., stimulus for and conditions of peroxidation) modulate MDA formation from lipid. Additional factors (e.g., TBA-test reagents and constituents) have profound effects on test response to fatty peroxide-derived MDA. The TBA test is intrinsically nonspecific for MDA; nonlipid-related materials as well as fatty peroxide-derived decomposition products other than MDA are TBA positive. These and other considerations from the extensive literature on MDA. TBA reactivity, and oxidative lipid degradation support the conclusion that MDA determination and the TBA test can offer, at best, a narrow and somewhat empirical window on the complex process of lipid peroxidation. The MDA content and/or TBA reactivity of a system provides no information on the precise structures of the "MDA precursor(s)," their molecular origins, or the amount of each formed. Consequently, neither MDA determination nor TBA-test response can generally be regarded as a diagnostic index of the occurrence/extent of lipid peroxidation, fatty hydroperoxide formation, or oxidative injury to tissue lipid without independent chemical evidence of the analyte being measured and its source. In some cases, MDA/TBA reactivity is an indicator of lipid peroxidation; in other situations, no qualitative or quantitative relationship exists among sample MDA content, TBA reactivity, and fatty peroxide tone. Utilization of MDA analysis and/or the TBA test and interpretation of sample MDA content and TBA test response in studies of lipid peroxidation require caution, discretion, and (especially in biological systems) correlative data from other indices of fatty peroxide formation and decomposition.
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            Autoxidation of polyunsaturated fatty acids: II. A suggested mechanism for the formation of TBA-reactive materials from prostaglandin-like endoperoxides.

            The nature and mechanism of formation of the thiobarbituric acid (TBA)-reaction material produced in the autoxidation of polyunsaturated fatty acids (PUFA) or their esters has been studied. On the basis of chemical studies and spectroscopic evidence, it is concluded that the TBA test detects malonaldehyde which arises at least in part from the acid-catalyzed or thermal decomposition or endoperoxides (2,3-dioxanorbornane compounds). These endoperosides have structures related to those of the endoperoxides produced in the biosynthetic sequence leading to prostaglandins. A mechanism is proposed in which these endoperoxides are formed in a free radical cyclization process operating in competition with hydroperoxide formation during the autoxidation of PUFA or their esters containing three or more double bonds. When 20:3 or 20:4 PUFA undergo autoxidation, some of the natural, physiologically active prostaglandins would be produced, although in very low yield, along with many other stereo- and positional isomers. Thus, it is possible that some of the complex symptoms of lipid peroxidation in vivo could be due to nonenzymatically produced prostaglandins or their steroisomers.
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              [33] Overview of methods used for detecting lipid peroxidation

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                Author and article information

                Journal
                Free Radical Biology and Medicine
                Free Radical Biology and Medicine
                Elsevier BV
                08915849
                January 1996
                January 1996
                : 20
                : 2
                : 251-256
                Article
                10.1016/0891-5849(95)02043-8
                8746446
                c7d75f04-823f-436c-a123-a9d25cfec6ee
                © 1996

                http://www.elsevier.com/tdm/userlicense/1.0/

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