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Figure 4.28. Oxidation of Arg by OH radical (adapted from xu and chance [261] with
the permission of the American chemical Society).
O
O
N
O
O
O
N
N
N
O
N
N
HO /O 2
+
O +
+
+
O
O
O
HN
NH
N NH
H
NH
OH
O
NH 2
H
O
O
+16 Da
-22 Da
-23 Da
+5 Da
-10 Da
Figure 4.29. Oxidation of His by OH radical (adapted from xu and chance [261] with
the permission of the American chemical Society).
the reactions, OH initially attacks the imidazole ring of His at positions c-2,
c-4, or c-5 and generates allyl-type radicals by OH addition. These radicals
were confirmed by continuous-flow EPR experiments [346]. Significantly, allyl
radicals can easily incorporate O 2 and yielded peroxy radicals. Further reaction
of the peroxy radicals gave a mixture of products such as asparagines, aspartic
acid, and 2-oxohistidine [343, 347-350]. Reaction conditions and the sequence
of the local amino acid determine products of oxidation of His by OH.
Aromatic Side Chains. Oxidation of Trp by OH is complicated and oxidized
products contain mass shifts of +16, +32, +4, and +20 Da, as determined in
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