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ESR Spin Trapping of the Reaction Between Urate and Peroxynitrite: the Hydrogen Adduct

机译:尿酸盐和过氧亚硝酸盐之间反应的ESR自旋阱:氢加合物

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Under basic conditions, the hydrogen adduct of the spin traps N-t-butyl-phenylnitrone (PBN) and alpha-(4-pyridyl-1-oxide)-N-t-butylnitrone (POBN) is formed as a major product in the reaction between the urate anion or dianion and peroxynitrite. It shows a characteristic nine-line spectrum with an intensity pattern of (1:2:1:1:2:1:1:2:1) and hyperfine splitting constants of a(H) = 10.68 G (two magnetically equivalent protons) and a(N) = 16.64 G. The hydrogen adduct of PBN also forms in the absence of urate. In this case, its formation is proposed to follow the non-traditional "inverted spin trapping" mechanism, followed by electron transfer between spin traps and the PBN-OH (or POBN-OH) adduct or one of its decomposition products. The H adduct formation is amplified when uric acid and peroxynitrite are present. Different yields of H adducts obtained from various spin traps supported the inverted spin trapping mechanism and can be rationalized by the relative redox potential of the spin traps.
机译:在碱性条件下,自旋捕集阱的氢加合物是尿酸盐之间反应的主要产物,形成的主要产物是N-叔丁基苯基硝酮(PBN)和α-(4-吡啶-1-氧化物)-Nt-丁基硝酮(POBN)。阴离子或双阴离子和过氧亚硝酸盐。它显示了特征性的九线谱,其强度模式为(1:2:1:1:2:1:1:2:1),超精细分裂常数为a(H)= 10.68 G(两个磁当量质子)和a(N)= 16.64G。在无尿酸盐的情况下也会形成PBN的氢加合物。在这种情况下,建议其形成遵循非传统的“反向自旋俘获”机制,然后在自旋俘获器与PBN-OH(或POBN-OH)加合物或其分解产物之一之间进行电子转移。当存在尿酸和过亚硝酸盐时,H加合物的形成会增加。从各种自旋阱获得的H加合物的不同收率支持了反向自旋阱机理,并且可以通过自旋阱的相对氧化还原电势来合理化。

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